Lead pollution recorded in Greenland ice indicates European emissions tracked plagues, wars, and imperial expansion during antiquity.

Lead pollution in Arctic ice reflects midlatitude emissions from ancient lead-silver mining and smelting. The few reported measurements have been extrapolated to infer the performance of ancient economies, including comparisons of economic productivity and growth during the Roman Republican and Imperial periods. These studies were based on sparse sampling and inaccurate dating, limiting understanding of trends and specific linkages. Here we show, using a precisely dated record of estimated lead emissions between 1100 BCE and 800 CE derived from subannually resolved measurements in Greenland ice and detailed atmospheric transport modeling, that annual European lead emissions closely varied with historical events, including imperial expansion, wars, and major plagues. Emissions rose coeval with Phoenician expansion, accelerated during expanded Carthaginian and Roman mining primarily in the Iberian Peninsula, and reached a maximum under the Roman Empire. Emissions fluctuated synchronously with wars and political instability particularly during the Roman Republic, and plunged coincident with two major plagues in the second and third centuries, remaining low for >500 years. Bullion in silver coinage declined in parallel, reflecting the importance of lead-silver mining in ancient economies. Our results indicate sustained economic growth during the first two centuries of the Roman Empire, terminated by the second-century Antonine plague.

Environmental Impact of Alkyl Lead(IV) Derivatives: Perspective after Their Phase-out.

The use of alkyl lead derivatives as antiknock agents in gasoline can be considered as one of the main pollution disasters of the 20th century because of both the global character of the pollution emitted and the seriousness of the impact on human health. Alkyl lead derivatives in themselves cannot be considered to be persistent pollutants because they readily degrade either before being released from the tailpipes or soon afterwards in the atmosphere. However, the inorganic lead they produced has been deposited in soils all over the planet, largely, but not exclusively in urban areas and along motorways, since the direct emission of lead into the atmosphere favored its dispersal over great distances: The signal of the massive use of alkyl lead derivatives has been found all over the world, including in remote sites such as polar areas. The short residence time of lead in the atmosphere implies that this compartment is highly responsive to changes in emissions. This was demonstrated when leaded gasoline was phased-out and is in striking contrast to the very long permanence of inorganic lead in soils, where resuspension is a permanent source of toxic lead.

Spatial distribution and historical trends of heavy metals in the sediments of petroleum producing regions of the Beibu Gulf, China.

The concentrations of As, Sb, Hg, Pb, Cd, and Ba in the surface and core sediments of the oil and gas producing region of the Beibu Gulf were measured by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES), Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Atomic Fluorescence Spectrometry (AFS), and the spatial distribution and historical trends of these elements are discussed. The results show that the concentrations of these elements are highest near the platforms. The results of Enrichment Factor (EF) and Potential Ecological Risk Index (PERI) also reveal significantly higher enrichment around the platforms, which imply that the offshore petroleum production was the cause of the unusual distribution and severe enrichment of these elements in the study area. The environment around the platforms was highly laden with toxic elements, thereby representing a very high ecological risk to the environment of the study area.

Source apportionment of polycyclic aromatic hydrocarbons (PAHs) into Central Park Lake, New York City, over a century of deposition.

Relative contributions of polycyclic aromatic hydrocarbons (PAHs) from combustion sources of wood, petroleum, and coal were computed in sediments from Central Park Lake in New York City (NY, USA) by chemical mass balance based on several reliable source indicators. These indicators are the ratio of retene to the sum of retene and chrysene, the ratio of 1,7-dimethylphenanthrene (DMP) to 1,7-DMP and 2,6-DMP, and the ratio of fluroanthene to fluroanthene and pyrene. The authors found that petroleum combustion-derived PAH fluxes generally followed the historical consumption data of New York State. Coal combustion-derived PAH flux peaked approximately in the late 1910s, remained at a relatively high level over the next 3 decades, then rapidly declined from the 1950s to the 1960s; according to historical New York State coal consumption data, however, there was a 2-peak trend, with peaks around the early 1920s and the mid-1940s. The 1940s peak was not observed in Central Park Lake, most likely because of the well-documented shift from coal to oil as the major residential heating fuel in New York City during the late 1930s. It was widely believed that the decreased PAH concentrations and fluxes in global sediments during the last century resulted from a major energy shift from coal to petroleum. The data, however, show that this shift occurred from 1945 through the 1960s and did not result in an obvious decline. The sharpest decrease, which occurred in the 1970s was not predominantly related to coal usage but rather was the result of multiple factors, including a decline in petroleum usage largely, the introduction of low sulfur-content fuel in New York City, and the introduction of emission-control technologies.

Relationship between polycyclic aromatic hydrocarbons (PAHs) and particle size in dated core sediments in Lake Lianhuan, Northeast China.

Atmospheric particle associated with pyrogenic polycyclic aromatic hydrocarbons (PAHs) poses serious threats to human health by inhalation exposure, especially in semiarid areas. Hence, the distributions of PAHs and particle size in two core sediments collected from Lake Lianhuan, Northeast China were studied. The sediments were dated radiometrically, and particle size distribution and PAH concentration were evaluated and potential human health risk was assessed. From 1980 to 2007, the dominant PAHs in the two cores were 2- and 3-ring PAHs, and the concentrations of 3-6 ring PAHs gradually increased from the early 1990s. Diagnostic ratios indicated that pyrogenic PAHs were the main sources of PAHs which changed over time from combustions of wood and coal to liquid fossil fuel sources. Fine particles (<65 µm) were the predominant particle size (56-97%). Lacustrine source (with the peak towards 200-400 µm) and eolian sources derived from short (2.0-10 and 30-65 µm) and long (0.4-1.0 µm) distance suspension were indentified from frequency distribution pattern of particle size. Significant correlations between 3-6 ring PAHs (especially carcinogenic 5-6 ring PAHs) and 10-35 µm particulate fractions indicated that eolian particles played an important role in adsorbing pyrogenic PAHs. Petroleum source of PAHs was only identified during the 1980s in one core sediments, in which positive correlations between 2-ring PAHs and particulate fractions of >125 µm were found. Future research should focus on the seven carcinogenic pyrogenic PAHs due to a rapidly increasing trend since 1995 based on the assessment of toxic equivalency factors.

A brief history of phosphorus: from the philosopher's stone to nutrient recovery and reuse.

The element phosphorus has no substitute in sustaining all life and food production on our planet. Yet today's phosphorus use patterns have resulted in both a global environmental epidemic of eutrophication and led to a situation where the future availability of the world's main sources of phosphorus is uncertain. This paper examines the important history of human interference with the phosphorus cycle from initial discovery to present, highlighting key interrelated events and consequences of the Industrial Revolution, Sanitation Revolution and Green Revolution. Whilst these events led to profound advances in technology, public health and food production, they have fundamentally broken the global phosphorus cycle. It is clear a 'Fourth Revolution' is required to resolve this dilemma and ensure humanity can continue to feed itself into the future while protecting environmental and human health.

Contaminated lead environments of man: reviewing the lead isotopic evidence in sediments, peat, and soils for the temporal and spatial patterns of atmospheric lead pollution in Sweden.

Clair Patterson and colleagues demonstrated already four decades ago that the lead cycle was greatly altered on a global scale by humans. Moreover, this change occurred long before the implementation of monitoring programs designed to study lead and other trace metals. Patterson and colleagues also developed stable lead isotope analyses as a tool to differentiate between natural and pollution-derived lead. Since then, stable isotope analyses of sediment, peat, herbaria collections, soils, and forest plants have given us new insights into lead biogeochemical cycling in space and time. Three important conclusions from our studies of lead in the Swedish environment conducted over the past 15 years, which are well supported by extensive results from elsewhere in Europe and in North America, are: (1) lead deposition rates at sites removed from major point sources during the twentieth century were about 1,000 times higher than natural background deposition rates a few thousand years ago (~10 mg Pb m(-2) year(-1) vs. 0.01 mg Pb m(-2) year(-1)), and even today (~1 mg Pb m(-2) year(-1)) are still almost 100 times greater than natural rates. This increase from natural background to maximum fluxes is similar to estimated changes in body burdens of lead from ancient times to the twentieth century. (2) Stable lead isotopes ((206)Pb/(207)Pb ratios shown in this paper) are an effective tool to distinguish anthropogenic lead from the natural lead present in sediments, peat, and soils for both the majority of sites receiving diffuse inputs from long range and regional sources and for sites in close proximity to point sources. In sediments >3,500 years and in the parent soil material of the C-horizon, (206)Pb/(207)Pb ratios are higher, 1.3 to >2.0, whereas pollution sources and surface soils and peat have lower ratios that have been in the range 1.14-1.18. (3) Using stable lead isotopes, we have estimated that in southern Sweden the cumulative anthropogenic burden of atmospherically deposited lead is ~2-5 g Pb m(-2) and ~1 g Pb m(-2) in the "pristine" north. Half of this cumulative total was deposited before industrialization. (4) In the vicinity of the Rönnskär smelter in northern Sweden, a major point source during the twentieth century, there is an isotopic pattern that deviates from the general trends elsewhere, reflecting the particular history of ore usage at Rönnskär, which further demonstrates the chronological record of lead loading recorded in peat and in soil mor horizons.

Slightly weathered Exxon Valdez oil persists in Gulf of Alaska beach sediments after 16 years.

Oil stranded by the 1989 Exxon Valdez spill has persisted in subsurface sediments of exposed shores for 16 years. With annualized loss rates declining from approximately 68% yr(-1) prior to 1992 to approximately 4% yr(-1) after 2001, weathering processes are retarded in both sediments and residual emulsified oil ("oil mousse"), and retention of toxic polycyclic aromatic hydrocarbons is prolonged. The n-alkanes, typically very readily oxidized by microbes, instead remain abundant in many stranded emulsified oil samplesfrom the Gulf of Alaska. They are less abundant in Prince William Sound samples, where stranded oil was less viscous. Our results indicate that, at some locations, remaining subsurface oil may persist for decades with little change.

Evolution of the international workshops on quantitative structure-activity relationships (QSARs) in environmental toxicology.

This presentation will review the evolution of the workshops from a scientific and personal perspective. From their modest beginning in 1983, the workshops have developed into larger international meetings, regularly held every two years. Their initial focus on the aquatic sphere soon expanded to include properties and effects on atmospheric and terrestrial species, including man. Concurrent with this broadening of their scientific scope, the workshops have become an important forum for the early dissemination of all aspects of qualitative and quantitative structure-activity research in ecotoxicology and human health effects. Over the last few decades, the field of quantitative structure/activity relationships (QSARs) has quickly emerged as a major scientific method in understanding the properties and effects of chemicals on the environment and human health. From substances that only affect cell membranes to those that bind strongly to a specific enzyme, QSARs provides insight into the biological effects and chemical and physical properties of substances. QSARs are useful for delineating the quantitative changes in biological effects resulting from minor but systematic variations of the structure of a compound with a specific mode of action. In addition, more holistic approaches are being devised that result in our ability to predict the effects of structurally unrelated compounds with (potentially) different modes of action. Research in QSAR environmental toxicology has led to many improvements in the manufacturing, use, and disposal of chemicals. Furthermore, it has led to national policies and international agreements, from use restrictions or outright bans of compounds, such as polychlorinated biphenyls (PCBs), mirex, and highly chlorinated pesticides (e.g. DDT, dieldrin) for the protection of avian predators, to alternatives for ozone-depleting compounds, to better waste treatment systems, to more powerful and specific acting drugs. Most of the recent advances in drug development could not have been achieved without the use of QSARs in one form or another. The pace of such developments is rapid and QSARs are the keystone to that progress. These workshops have contributed to this progress and will continue to do so in the future.

Synthesizing bioaccumulation data from the German metals in mosses surveys and relating them to ecoregions.

The European Heavy Metals in Mosses Surveys measure and map environmental concentrations of metals at more than 7000 sites in Europe. In Germany, moss samples were taken at 592 sites in 1990, at 1026 sites in 1995, and at 1028 sites in 2000, where up to 40 metals were measured each time. This article is about how to calculate multi-metal indices from the site- and metal-specific monitoring data and how to link them with the natural regions (ecoregions) of Germany. The ecoregions were calculated with surface data on natural vegetation, elevation, soil texture and climate by means of Classification and Regression Trees (CART). The ecoregions were mapped by GIS and superimposed on a map of multi-metal bioaccumulation indices calculated by means of geostatistics and percentile statistics from the monitoring data. These indices integrate the concentrations of 8 metals measured in 1990, 1995, and 2000 or 12 metals from the 1995 and 2000 surveys, respectively, and the ecoregionalisation enables their geostatistical estimates to be grouped into 21 ecological land categories. This two-step aggregation revealed that, from 1990 to 2000, the multi-metal metal accumulation declined up to 80%, varying with the ecoregions. Based on the multi-metal accumulation index hot spots, the metal accumulation was mapped, ecoregionalised, and suggested for further ecotoxicological assessment. Thus, the approach helps to assess the metal bioaccumulation within ecoregions in a comprehensive and holistic manner over time, space, and metals. This data aggregation is of importance for the environmental reporting in Germany and within the framework of the international environmental information systems. Furthermore, ecoregions may help to plan and optimize monitoring networks. Because monitoring should measure and estimate not only the environmental concentrations of substances but also their impacts on ecoregions, the number of monitoring sites should be proportional to the areas covered by the ecoregions and located according to their spatial variation.

Comment on Martínez-García et al. "Heavy metals in human bones in different historical epochs".

Martínez-García et al. (Sci. Tot Env. 348:51-72) have examined heavy metal exposure of humans in the Cartagena region using analysis of archaeological bones. An analysis of the lead and iron levels they report shows that they are physiologically implausible and must therefore result from diagenesis. This, and analogy with the known diagenetic origin of certain other elements, suggests that the other metal analyses they report are also unlikely to be in vivo concentrations. Lifetime heavy metal exposure cannot be deduced from diagenetically altered concentrations.

Lithogenic, oceanic and anthropogenic sources of atmospheric Sb to a maritime blanket bog, Myrarnar, Faroe Islands.

Antimony concentrations were measured in a core collected from Myrarnar, a blanket bog on the Faroe Islands which has been accumulating peat for more than six thousand years. The vertical distribution of Sb indicates that it has been supplied to the peat exclusively from the atmosphere. Despite the proximity to the ocean, the contribution of Sb to the peat from marine aerosols amounts to less than ca. 10% of the natural inputs. Although the peat core contains four notable layers of volcanic ash originating from Iceland, these have not contributed significantly to the Sb inventory. However, the distribution of Sb closely resembles that of Pb, with most of the Sb found in peats dating from the industrial period. Peat samples dating from the Roman Period are not only contaminated with Pb, but also with Sb. Lead is known to be immobile in peat bogs, and in Europe has been derived predominantly from industrial sources for thousands of years. The correlation between Sb and Pb in the peat core from the Faroe Islands supports the hypothesis that Sb is also effectively immobile in peat, and that ombrotrophic bogs are faithful archives of atmospheric Sb deposition. The data presented here also reinforces the view that natural Sb inputs during the past two centuries are dwarfed by industrial inputs, and that human activities have affected the atmospheric Sb cycle to a comparable extent to that of Pb. The natural rate of atmospheric Sb deposition recorded by the peat core (0.33 microg m(-2) year(-1)) is remarkably similar to the value obtained from a Swiss peat bog (Etang de la Gruère) in the samples dating from ca. 6000 to 9000 years ago (0.35 microg m(-2) year(-1)) which suggests that the background rates obtained from the peat cores have broader validity. Consistent with previous work, the data from the Faroe Islands suggests that the natural flux of Sb to the global atmosphere may have been overestimated by a factor of ten, and that the influence of human activities has been underestimated to the same extent.

Heavy metals in human bones in different historical epochs.

The concentration of the metals lead, copper, zinc, cadmium and iron was determined in bone remains belonging to 30 individuals buried in the Region of Cartagena dating from different historical periods and in eight persons who had died in recent times. The metals content with respect to lead, cadmium and copper was determined either by anodic stripping voltammetry or by atomic absorption spectroscopy on the basis of the concentrations present in the bone remains. In all cases, zinc and iron were quantified by means of atomic absorption spectroscopy. The lead concentrations found in the bone remains in our city are greater than those reported in the literature for other locations. This led to the consideration of the sources of these metals in our area, both the contribution from atmospheric aerosols as well as that from the soil in the area. Correlation analysis leads us to consider the presence of the studied metals in the analysed bone samples to be the consequence of analogous inputs, namely the inhalation of atmospheric aerosols and diverse contributions in the diet. The lowest values found in the studied bone remains correspond to the Neolithic period, with similar contents to present-day samples with respect to lead, copper, cadmium and iron. As regards the evolution over time of the concentrations of the metals under study, a clear increase in these is observed between the Neolithic period and the grouping made up of the Bronze Age, Roman domination and the Byzantine period. The trend lines used to classify the samples into 7 periods show that the maximum values of lead correspond to the Roman and Byzantine periods. For copper, this peak is found in the Byzantine Period and for iron, in the Islamic Period. Zinc shows an increasing tendency over the periods under study and cadmium is the only metal whose trend lines shows a decreasing slope.

Human lead exposure in England from approximately 5500 BP to the 16th century AD.

Lead concentration and isotope ratio data are presented for the tooth enamel of 77 individuals buried in England and spanning approximately 5000 years from the Neolithic until the 16th century AD. Whereas other tissues may be affected by diagenesis in the burial environment, the Pb concentration of tooth enamel is directly related to childhood exposure. This record is preserved post-mortem and over archaeological time. Tooth enamel Pb concentrations in the prehistoric period appear to be variable within the range 0.04 to approximately 0.4 ppm, with occasional higher levels. The Romano-British and medieval periods show a marked increase in Pb exposures with enamel concentrations reaching up to approximately 40 ppm. These exposures would today be associated with industrial pollution. Exposures appear to be highly variable compared with modern people, however, with many medieval individuals having very low enamel Pb concentrations comparable with prehistoric people. Lead isotope data refine this picture. We distinguish between the diverse isotopic ratios we believe to be characteristic of 'natural' exposure to Pb-from geological sources via the diet-and the much narrower isotopic range characteristic of exposure to technological Pb from ore sources. Taken together the data suggest that the maximum concentrations associated with 'non-technological' exposure at any period are approximately 0.5-1.0 ppm, similar to that reported for modern people in England.