Spatial and temporal variations of heavy metal contamination in sediments of a mangrove swamp in Hong Kong

Spatial and temporal variations of heavy metal contamination in sediments of a small mangrove stand in Hong Kong were examined by laying two transects perpendicular across the shore. Surface sediment samples were taken along the two transects running landward to seaward at intervals of 5 or 10 m during December 1989, and March, July and September 1990. Total concentrations of Cu, Zn, Mn and Pb did not show any specific trend along each transect, although the maximum concentration of heavy metals tended to occur at the landward edge. There was a high level of variability among locations within each transect; for instance, the Cu concentrations fluctuated from 1 to 42 μg g⁻¹. Certain sites contained exceptionally high levels of total metals. Total concentrations of Cu, Zn, Mn and Pb as high as 42, 150, 640 and 650 μg g⁻¹, respectively, were recorded, implying contaminated sediment. A comparison of the two transects indicated that the sediments of Transect B seemed to contain higher total Zn but lower Cu and Mn concentrations than those of Transect A. Most of the heavy metals accumulated in the sediments were not extractable with ammonium acetate and no Cu or Pb was detected in these extracts. The concentrations of extractable Zn and Mn were low, less than 10% of the total metal concentration in the sediment, and appeared to decrease from the landward to seaward samples. For both total and extractable metals, there were significant seasonal fluctuations for both transects, but no specific trends could be identified. These spatial and temporal variations suggest that the scale and representativeness of sampling require careful planning, and a single sample might not give a satisfactory evaluation of the levels of heavy metal contamination in mangrove ecosystems.     

Spatial patterns of submerged macrophytes and heavy metals in the hypertrophic, contaminated, shallow reservoir Lake Qattieneh/Syria

Our investigation on macrophytes in Lake Qattieneh, a large, shallow reservoir in western Syria, is a first assessment of ecological status of this lake. We studied spatial distribution patterns of aquatic macrophyte vegetation and heavy metal concentrations to determine if they can be used as indicators of point sources of pollution. Industrial and municipal point sources at the lake shore increase nutrient load and contamination by heavy metals. Water analyses revealed high concentrations of some heavy metals at some littoral sites: Ni 88.7 μg L⁻¹, Cr 49.99 μg L⁻¹, Co 14.38 μg L⁻¹, and Cu 11.65 μg L⁻¹. Despite hypertrophic conditions and high heavy metal contamination, we recorded several submerged macrophyte species with heterogeneous spatial distribution patterns. Whereas Potamogeton pectinatus L. dominates in the eastern part of the lake, near industrial point sources, both Myriophyllum spicatum L. and Potamogeton lucens L. form extended patches in the western part of the lake. The shallow, littoral areas near villages are dominated by Ranunculus trichophyllus Chaix in Villars and Ceratophyllum demersum L. The west-east gradient in nutrient and heavy metal concentrations in waters and sediments are reflected by the spatial distribution of submersed species. While the heavy metal concentrations of the water body vary considerably in different seasons, the contents in submersed macrophytes integrate seasonal variations of longer time periods. Spatial distribution and tissue accumulation of littoral macrophyte species reflect the environmental conditions at respective sites such as heavy metal contents in water and sediment.     

Trace elements in the sediments of a large Mediterranean marina (Port Camargue,France): Levels and contamination history

The study of trace elements (Cu, Zn, Pb, As, Hg) and butyltin concentrations in the sediments of Port Camargue enabled assessment of the levels and history of the contamination of the largest European marina linked with the use of antifouling paints. Surface sediments near the boat maintenance area were heavily contaminated with up to 1497 μg g⁻¹ of Cu, 475 μg g⁻¹ of Zn, 0.82 μg g⁻¹ of Hg, 94 μg g⁻¹ of Pb and over 10,000 ngSn g⁻¹ of tributyltin (TBT). High concentrations of Hg and TBT indicate ongoing sources of these elements despite the ban on their use as biocides in paints. Sediment cores provided records of contamination since 1969. The peak concentrations of As, Hg, Pb and TBT in the sediment profile reflect their presence on boat hulls when the marina was built at the end of the 1960s. Degradation of TBT in the sediments near the boat maintenance area is slow compared to other less contaminated area of the marina.     

Baseline heavy metals and metalloid values in blood of loggerhead turtles (Caretta caretta) from Baja California Sur, Mexico

Environmental pollution due to heavy metals is having an increased impact on marine wildlife accentuated by anthropogenic changes in the planet including overfishing, agricultural runoff and marine emerging infectious diseases. Sea turtles are considered sentinels of ecological health in marine ecosystems. The objective of this study was to determine baseline concentrations of zinc, cadmium, copper, nickel, selenium, manganese, mercury and lead in blood of 22 clinically healthy, loggerhead turtles (Caretta caretta), captured for several reasons in Puerto López Mateos, Baja California Sur, Mexico. Zinc was the most prevalent metal in blood (41.89 μg g⁻¹), followed by Selenium (10.92 μg g⁻¹). The mean concentration of toxic metal Cadmium was 6.12 μg g⁻¹ and 1.01 μg g⁻¹ respectively. Mean concentrations of metals followed this pattern: Zn > Se > Ni > Cu > Mn > Cd > Pb and Hg. We can conclude that blood is an excellent tissue to measure in relatively non-invasive way baseline values of heavy metals in Caretta caretta.     

Anthropogenic lead concentrations and sources in Baltic Sea sediments based on lead isotopic composition

The Gulf of Gdańsk is influenced by heavy metals of anthropogenic origin. In this study, temporal concentration changes of Pb, Zn, Cd, and Cu were studied in six, 50 cm long sediment cores. The main aim of the study was to concentrate on the history of Pb fluxes and Pb isotopic composition (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb) to trace Pb sources. The lowest Pb concentrations (19 μg g⁻¹) were measured in sediments deposited circa 1860, while the highest Pb concentrations (63–147 μg g⁻¹) were measured in sediments deposited between 1960s and 70s. Pre-industrial Pb fluxes were 7 Pb m² year⁻¹, while after WWII they reached 199 Pb m² year⁻¹. Highest ²⁰⁶Pb/²⁰⁷Pb ratios (∼1.22) were measured in the oldest sediment layers, and the lowest ²⁰⁶Pb/²⁰⁷Pb ratios (∼1.165) were measured in the sediments deposited in 1970s–90s. During the period of highest Pb contamination, the anthropogenic Pb fraction reached up to 93%. A general discussion of the Pb sources, emissions, and loads for Poland is included.     

Temporal and spatial biomonitoring of heavy metals in eastern Aegean coastal waters using Amphibalanus amphitrite

This biomonitoring study presents the spatial and temporal distributions of heavy metals in the soft tissues of a major fouling species Amphibalanus amphitrite living on hard substrate at different sites along the eastern Aegean coast. A. amphitrite has been chosen as a strong candidate for monitoring heavy metals. Sediment and seawater samples were also collected to detect their metal contents in order to gain more information on the environmental conditions and possible bioaccumulation patterns. The physico-chemical characteristics of sampling stations have been measured in order to characterize the sampling area. The order of metal concentrations in barnacles, sediment and seawater decreased in the following order Cu > Fe > Zn > Mn > Cd > Cr > Pb > Hg, Fe > Mn > Zn > Cu > Pb > Cr > Hg > Cd and Fe > Zn > Mn > Cu > Pb > Cr > Cd > Hg, respectively. These results showed that barnacles accumulate Cu in a higher degree than both sediment and seawater. Moreover, metal concentrations in barnacle have the potential for use in any future regulatory framework monitoring and eventually controlling ambient metal pollution levels.     

Historical record of metal accumulation and lead source in the southeastern coastal region of Korea

Concentrations of heavy metals and Pb isotopes were measured in the 1-M HCl leaching fraction of core sediments spanning the last 400 years. This sedimentary record of pollution history in metal concentrations shows a good correlation with the increases in industrialization, urbanization, and energy consumption since 1901s. Notably, the Pb concentration and the ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb ratios were constant before the 1910s (16.7 μg/g, 0.844, and 2.098, respectively), whereas they increased steadily up to 21.9 μg/g, 0.848, and 2.101 after the 1910s. The correlations between Pb isotope ratios (²⁰⁶Pb, ²⁰⁷Pb, and ²⁰⁸Pb) showed different linear regression trends for core sediments before and after the 1910s, indicating differences in Pb sources. Our interpretation suggests that the source of anthropogenic Pb in Korean coastal region and the Yellow Sea shelf was presumed to be Chinese coals or ores, which have also played a major role as sources of atmospheric particulate Pb.     

Biomonitoring of organochlorine compounds and trace metals along the Eastern Adriatic coast (Croatia) using Mytilus galloprovincialis

The paper presents the results of monitoring trace organic contaminants (17 PCBs and 7 OCPs) and 6 trace metals (Cd, Cr, Cu, Hg, Pb and Zn) in the coastal waters of the eastern Adriatic in 2006 using Mytilus galloprovincialis as indicator species. OCPs were found in all samples (0.07-14.3 ng g⁻¹ d.wt.), while in positive samples concentrations of PCBs ranged between 0.16 and 20.5 ng g⁻¹ d.wt. The α-HCH/γ-HCH and DDE/DDT ratios indicated recent input of γ-HCH and DDT. Spatial distributions of HCB, PCBs, DDTs and Hg were significantly correlated with population density. Although elevated concentrations of all trace metals and organic contaminants were recorded in the densely populated and industrialized areas, overall data point to relatively low level of contamination of the eastern Adriatic coast. Evaluation of the risks to human health associated with consumption of the mussels suggested that there is no health risk for moderate shellfish consumers.     

Long term trends of Hg uptake in resident fish from a polluted estuary

Mercury contamination of fish is dependent upon a system’s ability to transform inorganic Hg into biologically available forms; however, fish biometrics also play an important role. To assess long term trends in Hg concentrations in sand flathead (Platycephalus bassensis) a polynomial model, corrected for fish length, was used to evaluate temporal trends and spatial variability, while growth rates were estimated using the Von Bertalanffy length-at-age model. Hg concentrations showed no decrease over time, and generally remained near recommended consumption levels (0.5 mg kg⁻¹). Previously reported spatial differences in Hg concentrations were not supported by the data once the models were corrected for fish length. Growth rate variation accounted for a large part of the previously published spatial differences. These results suggest that inclusion of fish biometrics is necessary to facilitate an accurate interpretation of spatial and temporal trends of contaminant concentrations in long term estuarine and marine monitoring programs.     

The application of lead isotope ratios in the Antarctic macroalga Iridaea cordata as a contaminant monitoring tool

Lead (Pb) isotope ratios were measured in the marine macroalga Iridaea cordata collected from four locations in the Windmill Islands, East Antarctica. Based on the masses of thalli collected, samples analysed in this study were likely to be a mixture of one and two year old thalli. For a sample of thalli of various ages (<12 months to 2 years old) from the same site there was no apparent variation in Pb concentration or Pb isotope ratio with thallus mass/age, indicating that contaminant sources had been constant over the lifetime of the thalli sampled. I.cordata samples close to the Thala Valley waste disposal site (Brown Bay Inner) near the Australian Station, Casey, displayed isotopic signatures (²⁰⁸Pb/²⁰⁴Pb 35.99; ²⁰⁶Pb/²⁰⁷Pb 1.066; n = 3; average values shown) trending towards that possessed by major Australian Pb sources (Broken Hill and Mt Isa, ²⁰⁸Pb/²⁰⁴Pb 35.60; ²⁰⁶Pb/²⁰⁷Pb 1.041) suggesting that these samples had been exposed to anthropogenic Pb originating from the Thala Valley waste disposal site. Material collected hundreds of metres from the tip location at Brown Bay Outer had isotopic values (²⁰⁸Pb/²⁰⁴Pb 36.32; ²⁰⁶Pb/²⁰⁷Pb 1.088; n = 10) intermediate between Brown Bay Inner and sites further from the contaminant source at Sparkes Bay and Wilkes (²⁰⁸Pb/²⁰⁴Pb 36.46; ²⁰⁶Pb/²⁰⁷Pb 1.094; n = 4) showing that contaminant transport was predominantly restricted to Brown Bay Inner. This study demonstrates that the isotope ratios of Pb in marine macroalgae can provide valuable information as to the origin and extent of heavy metal flux in a marine environment.     

Lead in blood and eggs of the sea turtle, Lepidochelys olivacea, from the Eastern Pacific: Concentration, isotopic composition and maternal transfer

Concentrations of lead were assessed in the sea turtle, Lepidochelys olivacea, from a nesting colony of the Eastern Pacific. Twenty-five female turtles were sampled and a total of 250 eggs were collected during the “arribada” event of the 2005-2006 season. Considering the nesting season, the maternal transfer of lead (Pb) via egg-laying, in terms of metal burden in whole body, was 0.5%. Pb concentrations (in dry weight) in blood (0.95 ± 0.18 μg g⁻¹) and egg samples (yolk, 0.80 ± 0.10 μg g⁻¹; albumen, 1.08 ± 0.20 μg g⁻¹; eggshell, 1.05 ± 0.20 μg g⁻¹) were comparable or even lower than those found in other sea turtles. The isotope ratios (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁸Pb) in blood (1.183 ± 0.0006 and 2.452 ± 0.0006, respectively) were comparable to that of natural Pb-bearing bedrock in Mexico (1.188 ± 0.005 and 2.455 ± 0.008, respectively). According to international norms of Pb, the health of this population and its habitats is acceptable for Pb and corresponds to basic levels of a nearly pristine environment.     

Trace elements in tissues of cetacean species rarely stranded along the Israeli Mediterranean coast

In this paper we present the concentrations of Hg, Cd, Se, Pb, Cu, Mn, Zn and Fe in organs of 6 non-common specimens of cetaceans that were stranded along the Israeli Mediterranean coast (IMC), during 2002–2010: two fin whales, one minke whale, one Cuvier’s beaked whale, one rough-toothed dolphin, and one Risso’s dolphin. Most of the specimens were calves stranded by accident. Concentrations of Hg and Cd were low in tissues of the baleen whales and higher in the toothed whales, with maximum concentrations of 1067 mg kg⁻¹ Hg in the liver of the Risso’s dolphin and 29 mg kg⁻¹ Cd in the kidney of the Cuvier’s beaked whale. As far as we are aware, this is the first report of trace elements in baleen whales in the Eastern Mediterranean, and the first report of trace elements in minke whale and rough-toothed dolphin in the Mediterranean.     

Assessment of heavy metal contamination of roadside soils in Southwest China

Topsoil (0–20 cm) samples were collected from the edge of roads to the locations about 200 m off the roads along the four roads with different transportation periods in October 2005. Total concentrations of As, Cd, Cr, Cu, Ni, Pb and Zn were determined using the inductively coupled plasma atomic absorption spectrometry in order to assess and compare road transportation pollution. Results showed that with the exception of As, Cu and Pb, the average concentrations of heavy metals were generally, higher than the regional elemental background values. Most soil samples were moderately or highly polluted by Cd or Ni, but the contamination index (P _i ) values for As, Pb and Zn were lower than other heavy metals in all sites. Among the four roads, heavy metal pollution was heavier for Dali Road due to longer transportation periods, while low or no contamination could be observed for the other roads. However, the integrated contamination index (P _c ) values showed a generally low contamination or no contamination level for all soil samples in this region, followed by the order of Dali Road > Dabao Highway > Road 320 > Sixiao Highway. The same pollution source of these heavy metals was found using factor analysis.     

Spatial and temporal variations in trace metal concentrations in surface sediments of the Marennes Oléron Bay. Relation to hydrodynamic forcing

Sediments quality assessment is of priority concern to provide a comprehensible overview of ecological and chemical state of an ecosystem. The Marennes-Oléron Bay, hosting the largest oyster production in France, is influenced by the historic polymetallic pollution of the Gironde Estuary. Despite, management efforts and decreasing emissions in the Gironde watershed, Cd levels in oysters from the bay are close to consumption limit (5 μg g⁻¹ dw, EC no. 466/2001). In this context, the aim of the study was to assess the priority metal (Ni, Cu, Zn, As, Ag, Cd, Hg, Pb and Th) concentrations in sediment within the Bay, by investigating spatial and temporal distribution variations and the role of hydrodynamic forcing. For that we selected three sites (east, west and south) characterizing different environments of the Bay and we observed metal concentrations, grain size distribution, bed elevation and wave activities during a year survey. The sampling strategy pointed out both spatial and temporal metal concentrations variability in sediment. In general, metal enrichments were close to geochemical background. The eastern part of the Bay, largely influenced by the Charente river particulate deposition, presented constant concentrations over the survey. In contrast, in the western part, bed elevation was strongly influenced by hydrodynamic forcing especially wave activities, and metal distribution showed constant metal concentrations except very located Cd minor enrichment related to the Gironde influence via the Antioche Strait (north). The southern part was disconnected from the rest of the Bay and showed minor to very located moderately severe Cd enrichment, related to the Gironde water discharges via the Maumusson Strait (south). Thus, the multi-disciplinary approach was relevant to characterize the interactions between hydrodynamic forcing on the environment and sediments and their metal quality state which (i) were close to geochemical background over a year for Ni, Cu, Zn, As, Ag, Hg and Pb (i) which presented enrichment of Cd in the western and southern part.     

Sediment chemical contamination of a shallow water area close to the industrial zone of Porto Marghera (Venice Lagoon,Italy)

The industrial zone of Porto Marghera is one the most important “contaminated sites of national interest” (SIN) in Italy, being identified as an area of high environmental risk. The site includes a wide shallow water area of the Venice Lagoon extending toward the city of Venice, which was investigated in order to acquire information on the pollutant level and distribution. Grain-size, heavy metal, nutrient, and organic micropollutant concentrations were determined in the surface sediment layers (0–5 and 5–10 cm depths) of 51 sites. A generally low contamination was found, except for Hg concentration, which increases the toxicological risk in most of the sites of the area, according to the results of a comparison with Sediment Quality Guidelines. A heavy pollution fingerprint (Cd, Cu, Hg, Pb, and Zn up to 15.2, 257, 11.9, 248, and 3010 mg/kg d.w., respectively) was instead found near the Tresse Island, which is ascribed to the spill of pollutants from the contaminated sediment disposed therein. Grain-size and heavy metal profiles down to a depth of 40 cm in eight selected sites, finally show a probable decrease of the pollution affecting the area in recent years.     

Volcanic emissions of metals and halogens from White Island (New Zealand) and Erebus volcano (Antarctica) determined with chemical traps

Volcanic emission rates of As, Sb, Pb, Hg, Se, Cl, and F were determined at Erebus volcano, Antarctica and White Island, New Zealand, using chemical traps. The trace metal fluxes were determined by combining the species to S ratios in the solutions with SO₂ emission rates measured by correlation spectrometry at the two volcanoes. At Erebus volcano, fluxes for the metals Pb and Hg were 2.0 × 10^− 4 and 8.1 × 10^− 6 kg s^− 11, respectively. Fluxes for Cl, F, As, Sb and Se (0.35, 0.15, 2.5 × 10^− 4, 1.2 × 10^− 5, and 4.5 × 10^− 6 kg s^− 1, respectively) agreed within error limits for values determined previously by the LiOH impregnated filter method [Zreda-Gostynska, G., Kyle, P., Finnegan, D., Prestbo, K., 1997. Volcanic gas emissions from Mount Erebus and their impact on the Antarctic environment. Journal of Geophysical Research, 102(B7): 15039–15055.], demonstrating the utility of the chemical trap method. A fall in the As/S ratio from 7 × 10^− 4 in 1997/1999 to 3 × 10^− 4 in 2000 at Erebus coincided with a change in the frequency and style of eruptive activity that may have been due to injection of magma into the system. At White Island, chemical trap data indicated fluxes of Cl = 0.90, F = 0.0079, Pb = 2.7 × 10^− 4, Hg = 1.1 × 10^− 5, As = 1.3 × 10^− 4, Sb = 1.9 × 10^− 5 and Se = 1.5 × 10^− 5 kg s^− 1. Samples collected 600 m downwind of the active crater were comparable to samples collected adjacent to the main gas vent, showing that this method can still be used at some distance from a degassing vent.     

Contamination characteristics of heavy metals in wetland soils along a tidal ditch of the Yellow River Estuary, China

Surface soils (0–20 cm) were collected from along a tidal ditch of the Yellow River Estuary in August of 2007. Samples were subjected to a total digestion technique before they were analyzed for total concentrations of As, Cr, Cd, Cu, Ni, Pb, Zn, P and S in order to investigate heavy metal contamination levels in wetland soils nearby the tidal ditches and their main sources. Results showed that the mean concentrations of these heavy metals except for As and Cd were lower than the Class I criteria. Nearly all sampling sites showed lower contamination levels for As and Cd, while no contamination levels for other heavy metals. Cr, Cu, and Ni mainly originated from parent rocks, and Pb and As might originate from tidal seawater and oil field pollution, respectively; while Cd and Zn mainly originated from parent rocks and tidal seawater. Most of heavy metals showed significant correlations with total concentrations of P and S, however, no significant correlations were observed between them and soil pH, slat and soil organic matter.     

Export fluxes of biogenic matter in the presence and absence of seasonal sea ice cover in the Chukchi Sea

Drifting sediment traps were deployed at 9 stations in May-June (ice-covered conditions) and July-August (ice-free conditions) 2004 in the Chukchi Sea to investigate the variability in export fluxes of biogenic matter in the presence and absence of sea ice cover. Measurements of chlorophyll-a (Chl-a), particulate organic carbon (POC), particulate nitrogen (PN), phytoplankton, zooplankton fecal pellets, and the stable carbon isotope composition (δ¹³C) of the sinking material were performed along Barrow Canyon (BC) and a parallel shelf-to-basin transect from East Hanna Shoal (EHS) to the Canada Basin. POC export fluxes were similarly high in the presence (378±106 mg C m⁻² d⁻¹) and in the absence of ice cover (442±203 mg C m⁻² d⁻¹) at the BC stations, while fluxes were significantly higher in the absence (129±98 mg C m⁻² d⁻¹) than in the presence of ice cover (44±29 mg C m⁻² d⁻¹) at the EHS stations. The C/N ratios and δ¹³C values of sinking organic particles indicated that POC export fluxes on the Chukchi continental shelf were mostly composed of freshly produced labile material, except at the EHS stations under ice cover where the exported matter was mostly composed of refractory material probably advected into the EHS region. Chl-a fluxes were higher under ice cover than in ice-free water, however, relatively low daily loss rates of Chl-a and similar phytoplankton carbon fluxes in ice-covered and ice-free water suggest the retention of phytoplankton in the upper water column. An increase in fecal pellet carbon fluxes in ice-free water reflected higher grazing pressure in the absence of ice cover. Elevated daily loss rates of POC at the BC stations confirmed other indications that Barrow Canyon is an important area of carbon export to the basin and/or benthos. These results support the conclusion that there are large spatial and temporal variations in export fluxes of biogenic matter on the Chukchi continental shelf, although export fluxes may be similar in the presence and in the absence of ice cover in highly productive regions.     

Lead concentrations and isotopes in aerosols from Xiamen, China

To investigate the magnitude and origin of lead (Pb) pollution in the atmosphere of Xiamen, China, 40 aerosol samples were collected from the coast of Xiamen from January to December 2003. All these samples were measured for Pb isotopic compositions (²⁰⁸Pb/²⁰⁶Pb = 2.10897 ± 0.00297, ²⁰⁷Pb/²⁰⁶Pb = 0.85767 ± 0.00159, n = 40) using a Multi-collector-Inductively Coupled Plasma Mass Spectrometer (MC-ICPMS). Thirty-five out of forty samples were also measured for Pb concentrations (79.1 ± 38.3 ng/m³, n = 35) by Atomic Absorption Spectroscopy (AAS). The results indicate that the Pb concentrations display significant seasonal variations while Pb isotopic ratios remain relatively constant. The Pb concentrations were high in January and February, abruptly decreased in March, remained relatively constant (but low) from April to August, and then gradually increased from September to December. This corresponds to the rainless climate in winter and rain scavenging in summer. The higher Pb concentration of Xiamen aerosols in winter and spring may be also caused by long-range transferred anthropogenic Pb during the northeastern monsoon seasons. Although the use of leaded gasoline in Xiamen was banned in 2000, our new data indicate that the Pb annual concentrations of aerosols in Xiamen increased about 12% when compared to the data measured between 1991 and 1993. Thus, Pb pollution in the atmosphere of Xiamen has not receded even after the phase-out of leaded gasoline. Our results further confirm the previous studies’ conclusion that the primary source of atmospheric Pb in China, especially in South China, is the vast combustion of lead-containing coal, not leaded gasoline.     

The age of SNC meteorites and the antiquity of the Martian surface

We report new Sm-Nd, Lu-Hf, and Pb-Pb mineral and whole-rock isotope data for the basaltic shergottite Zagami, as well as Pb-Pb whole-rock isotope data for the basaltic shergottite Los Angeles, the lherzolitic shergottite Dar-al-Gani 476 (DaG 476), and the clinopyroxenite Nakhla. In agreement with previous findings, our new Sm-Nd and Lu-Hf mineral ages on the Martian meteorite Zagami are young (155 and 185 Ma, respectively). The ²⁰⁷Pb/²⁰⁶Pb-²⁰⁴Pb/²⁰⁶Pb compositions of the insoluble fractions of shergottites (Zagami, Los Angeles, and literature data for Shergotty and EETA79001) form an excellent alignment indicative of a 4.0 Ga crystallization age. The range of Pb isotope compositions observed in the leachates of these samples attests to negligible contamination of the shergottites by terrestrial Pb and argues against mixing relationships. The age of 4.048 ± 0.017 Ga (MSWD = 1.5) provided by the Pb isotope compositions of the Zagami whole-rock and residues is therefore taken to date the crystallization of this rock, which, so far, was believed to be only ∼ 180 Ma old. Based on this result, we argue that the lithosphere of Mars is extremely old and that most mineral ages were reset recently by acidic aqueous solutions percolating through the Martian surface. This interpretation is consistent with photographic interpretations of erosional features on Mars. It also relieves the constraint imposed by the presence of anomalies of ¹⁴²Nd and ¹⁸²W (both products of extinct radioactive nuclides) that the Martian mantle should have preserved primordial isotopic heterogeneities, thus allowing for the planet interior to be actively convecting.