Equilibrium and kinetic Si isotope fractionation factors and their implications for Si isotope distributions in the Earth’s surface environments

Several important equilibrium Si isotope fractionation factors among minerals, organic molecules and the H₄SiO₄ solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth’s surface environments. The results reveal that, in comparison to aqueous H₄SiO₄, heavy Si isotopes will be significantly enriched in secondary silicate minerals. On the contrary, quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution. The extent of ²⁸Si-enrichment in hyper-coordinated organosilicon complexes was found to be the largest. In addition, the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer was calculated, and the results support the previous statement that highly ²⁸Si-enrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations. With the equilibrium Si isotope fractionation factors provided here, Si isotope distributions in many of Earth’s surface systems can be explained. For example, the change of bulk soil δ³⁰Si can be predicted as a concave pattern with respect to the weathering degree, with the minimum value where allophane completely dissolves and the total amount of sesqui-oxides and poorly crystalline minerals reaches their maximum. When, under equilibrium conditions, the well-crystallized clays start to precipitate from the pore solutions, the bulk soil δ³⁰Si will increase again and reach a constant value. Similarly, the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain the δ³⁰Si variations in the ground water profile. The equilibrium Si isotope fractionations among the quadra-coordinated organosilicon complexes and the H₄SiO₄ solution may also shed light on the Si isotope distributions in the Si-accumulating plants.     

High precision Fe isotope measurement and applications in aquatic environmental studies

In aquatic environment, iron redox reaction may occur through a） microbial activity and b） photo-chemistry. Iron chemistry plays a significant role in the health of aquatic ecosystems. For example, Fe^2＋ is more mobile than Fe^3＋. Iron can be bound to dissolved organic carbon （DOC）, and when Fe^2＋ is oxidized to Fe^3＋ （biotically or abiotically）, Fe is precipitated and induce co-precipitation of the DOC. Furthermore, iron is a major nutrient to aquatic organisms. Because Fe^2＋ is more bioavailable than Fe^3＋, iron redox chemistry can be a controlling factor in biological production, such as algae bloom which can be a public health concern. Experiments have shown that Fe redox reactions, biotically or abiotically, can generate significant Fe isotope fraction among different Fe species. Accordingly, analysis of Fe isotope composition of phytoplanktons can be a valuable tool in studying Fe dynamics in ecosystems. Precise measurement of Fe isotope, however, presents some challenges. Recent advances in mass spectrometry, specifically high resolution MC-ICP-MS, allow measurement of Fe isotopes free of interferences.     

High-pressure neutron diffraction study on H–D isotope effects in brucite

A neutron powder diffraction study of hydrogenated and deuterated brucite was conducted at ambient temperature and at pressures up to 9 GPa, using a Paris–Edinburgh high-pressure cell at the WAND instrument of the ORNL High Flux Isotope Reactor. The two materials were synthesized by the same method and companion measurements of neutron diffraction were conducted under the same conditions. Our refinement results show that the lattice-parameters of the a axis, parallel to the sheets of Mg–O octahedra, decrease only slightly with pressure with no effect of H–D substitution. However, the c axis of Mg(OD)₂ is shorter and may exhibit greater compressibility with pressure than that of Mg(OH)₂. Consequently, the unit-cell volume of deuterated brucite is slightly, but systematically smaller than that of hydrogenated brucite. When fitted to a third-order Birch–Murnaghan equation in terms of the normalized unit-cell volume, values of the bulk modulus for hydrogenated and deuterated brucite (K ₀ = 39.0 ± 2.8 and 40.4 ± 1.3 GPa, respectively) are, however, indistinguishable from each other within the experimental errors. The measured effect of H–D substitution on the unit-cell volume also demonstrates that brucite (and other hydrous minerals) preferentially incorporate deuterium over hydrogen under pressure, suggesting that the distribution of hydrogen isotopes in deep-earth conditions may differ significantly from that in near-surface environments.     

Water geochemistry and boron isotope in the Xijiang River,SW China

During the last decade boron isotopic compositions have been successfully used as a geochemical tracer in oceanic paleo-pH reconstruction and paleo-climatologic studies. All the pH-proxy investigations were based on the assumption that the boron concentra…     

Environmental geochemistry of calcium isotopes： Applications of a new stable isotope approach

1IntroductionIn nature, calcium has six naturally occurring sta-ble isotopes with atomic mass units (amu) and the a-bundances of40Ca (96.941%),42Ca (0.647%),43Ca (0.135%),44Ca (2.086%),46Ca (0.004%)and48Ca (0.187%) are presented in this paper.These analyt…     

Synopsis of strontium isotope variations in groundwater at Äspö, southern Sweden

Strontium isotope ratios are used to identify end-member ground-water compositions at Äspö in southeastern Sweden where the Hard Rock Laboratory (HRL) has been constructed to evaluate the suitability of crystalline rock for the geologic disposal of nuclear waste. The Hard Rock Laboratory is a decline (tunnel) constructed in 1.8 Ga-old granitic rock that forms islands in an archipelago along the Swedish coast. Ground-water samples were obtained for isotopic analyses from boreholes drilled from the surface and from side boreholes drilled within the HRL. Infiltration at Äspö occurs primarily through fractures zones in the granitic bedrock beneath thin soils throughout the area. Because of extremely low Sr concentrations, rain and snow are not important contributors to the Sr isotope budget of the ground-water system. At shallow levels, water percolating downward along fractures and fracture zones acquires a δ⁸⁷Sr between +9.5 and +10.0‰ and maintains this value downward while Sr concentrations increase by two orders of magnitude. Ground-water samples from both boreholes and from in the HRL show the effects of mixing with saline waters containing as much as 59 mg/L Sr and δ⁸⁷Sr values as large as +13.9‰. Baltic Sea water is a potential component of the groundwater system with δ⁸⁷Sr values only slightly larger than modern marine values (+0.3‰) but with much lower concentrations (1.5 mg/L) than ocean water (8 mg/L). However, because of large Sr concentration differences between the saline groundwater (59 mg/L) and Baltic Sea water (1.5 mg/L), δ⁸⁷Sr values are not particularly sensitive indicators of sea-water intrusion even though their δ⁸⁷Sr values differ substantially.     

Hydrogen isotope of individual n-alkanes from modern sediments and their application to environments

Hydrogen isotopes are commonly fractionated to a much greater extent and as a result display larger variations in δ values, In terms of the hydrogen isotope ratios of individual n-alkanes of 16 samples of modern sediments selected from four different locations in the southern part of Gansu, China, the δD values for most of the n-alkanes varied from -150‰-300‰, Variations in δD also occurred between different ranges of n-alkanes, effects of environmental changes on the hydrogen isotopic compositions of individual n-alkanes have been detected. Besides the δD values of n-alkanes, the δD values of lipids including pristane （Pr）, phytane （Ph） were also examined, by the combination of D/H ratios with molecular fingerprinting, Our results further support the notion that hydrogen isotopes of n-alkanes from modern sediments can act as paleoclimatic and paleoenvironmental proxies and provide invaluable new sources of information in the research of paleoenvironment reconstruction.     

Is there a stable isotope evidence for the CO2 fertilization effect?

It has been suggested that part of the so-called “missing sink” of carbon dioxide introduced into the atmosphere by anthropogenic activities, that is the imbalance between estimated anthropogenic carbon dioxide emissions and oceanic uptake, may be stored in the vegetation in midlatitudes. Precise mechanisms of abstraction of additional carbon dioxide by vegetation, also known as the “fertilization effect”, are poorly understood. Stable carbon and hydrogen isotope ratios of cellulose extracted from annual growth rings (covering the time period 1980–1993) in an oak tree from Kalamazoo, SW Michigan provide a basis to investigate at a physiological level how the fertilization effect may operate. The carbon isotope ratios show that the intercellular concentration of carbon dioxide increased due to an increase in stomatal opening. Although increased intercellular concentration of carbon dioxide translated to increased Water Use Efficiency and assimilation rates, it also resulted in increased transpiration rate as shown by higher D/H of the fixed carbon. The two-fold significance of the isotope data are: first, they provide the first field evidence based on isotope studies for excess CO₂ induced biomass production and second, they suggest that this mechanism is likely to operate only in limited environments. Vegetation in regions where moisture availability is not restricted so that there can be a gain in water use efficiency despite increased leaf evaporation are best suited to sequester excess carbon from the atmosphere.     

New data on the Pb isotope composition of Noril’sk sulfide ores

Doklady Earth Sciences -     

Equilibrium thallium isotope fractionation and its constraint on Earth’s late veneer

Equilibrium isotope fractionation of thallium (Tl) includes the traditional mass-dependent isotope fractionation effect and the nuclear volume effect (NVE). The NVE dominates the overall isotope fractionation, especially at high temperatures. Heavy Tl isotopes tend to be enriched in oxidized Tl³⁺-bearing species. Our NVE fractionation results of oxidizing Tl⁺ to Tl³⁺ can explain the positive enrichments observed in ferromanganese sediments. Experimental results indicate that there could be 0.2–0.3 ε-unit fractionation between sulfides and silicates at 1650 °C. It is consistent with our calculation results, which are in the range of 0.17–0.38 ε-unit. Importantly, Tl’s concentration in the bulk silicate Earth (BSE) can be used to constrain the amount of materials delivered to Earth during the late veneer accretion stage. Because the Tl concentration in BSE is very low and its Tl isotope composition is similar with that of chondrites, suggesting either no Tl isotope fractionation occurred during numerous evaporation events, or the Tl in current BSE was totally delivered by late veneer. If it is the latter, the Tl-content-based estimation could challenge the magnitude of late veneer which had been constrained by the amount of highly siderophile elements in BSE. Our results show that the late-accreted mass is at least five-times larger than the previously suggested magnitude, i.e., 0.5 wt% of current Earth’s mass. The slightly lighter ²⁰⁵Tl composition of BSE relative to chondrites is probable a sign of occurrence of Tl-bearing sulfides, which probably were removed from the mantle in the last accretion stage of the Earth.

     

Cenomanian–Turonian carbon isotope stratigraphy of the Western Canadian Sedimentary Basin

The Cenomanian–Turonian boundary was characterized by distinctive positive carbon isotope excursions that were related to the formation of widespread oceanic anoxia. High-resolution geochemical proxies (TOC, CaCO₃, δ¹³C_org, and δ¹³C_carb) obtained from bulk rock, planktic foraminifers, and inoceramids from four marine marlstone-dominated stratigraphic sections in the Western Canada Sedimentary Basin (WCSB) were used to establish a regional carbon isotope stratigraphic framework and to investigate paleoenvironmental variability in four different depositional settings. Compared to background δ¹³C_org, (<−27‰) and δ¹³C_carb (<2‰) values which were correlative to stable isotope excursions during Oceanic Anoxic Event (OAE) II worldwide, the δ¹³C_org (>24‰), and δ¹³C_carb (>4‰) derived from inoceramid prisms in the studied sections within WCSB, were elevated during the Late Cenomanian–Early Turonian. During this interval, TOC and CaCO₃ values which increased sporadically to >40% and 7%, respectively, were not consistent enough to be used for stratigraphic correlations. Based on the δ¹³C_org excursions, two bentonite beds were regionally correlated across this portion of the Western Interior Seaway (WIS). The eruption associated with the “Red” bentonite occurred approximately coeval with the maximum δ¹³C_org-excursion during OAE II in the Neocardioceras juddii Zone, whereas the “Blue” bentonite coincides with the termination of OAE II in the latest Watinoceras devonense zone. During the Late Cenomanian–Early Turonian in the WCSB, benthic foraminifers were sparse or totally absent, indicating the existence of fully anoxic bottom-water conditions. Planktic foraminifera were common in the well-oxygenated surface waters. A benthic oxic zone characterized by several agglutinated species occurs in the eastern part of the WSCB at the beginning of OAE II in the Sciponoceras gracile zone. The termination of the OAE II in the WCSB coincides with the first occurrence of small ammonites (Subprionocyclus sp.) in the western part of the basin.     

Pressure responses of portlandite and H–D isotope effects on pressure-induced phase transitions

The pressure responses of portlandite and the isotope effect on the phase transition were investigated at room temperature from single-crystal Raman and IR spectra and from powder X-ray diffraction using diamond anvil cells under quasi-hydrostatic conditions in a helium pressure-transmitting medium. Phase transformation and subsequent peak broadening (partial amorphization) observed from the Raman and IR spectra of Ca(OH)₂ occurred at lower pressures than those of Ca(OD)₂. In contrast, no isotope effect was found on the volume and axial compressions observed from powder X-ray diffraction patterns. X-ray diffraction lines attributable to the high-pressure phase remained up to 28.5 GPa, suggesting no total amorphization in a helium pressure medium within the examined pressure region. These results suggest that the H–D isotope effect is engendered in the local environment surrounding H(D) atoms. Moreover, the ratio of sample-to-methanol–ethanol pressure medium (i.e., packing density) in the sample chamber had a significant effect on the increase in the half widths of the diffraction lines, even at pressures below the hydrostatic limit of the pressure medium.     

Helium and argon isotope geochemistry of natural gases in China’s petroliferous basins

The age-accumulation effect of 40Ar in hydrocarbon source rocks was discussed in accordance with the decay law of radioactive elements. In terms of the mean values of 40Ar/36Ar, the old Sinian gas reservoirs (mean values of 40Ar/36Ar: 7009) were definitely distinguished from the Permian gas reservoirs (mean values of 40Ar/36Ar: 1017) in Weiyuan, Sichuan Province, and the gas source of the Permian gas reservoir (mean values of 40Ar/36Ar: 5222) in well Wei-7 with the Weiyuan structure is defined as the Sinian system. Based on the values of 40Ar/36Ar, the coal-type gases (The source rocks are of the C-P system; mean values of 40Ar/36Ar: 1125) are definitely distinguished from the oil-type gases (The source rocks are of the Tertiary system; mean values of 40Ar/36Ar: 590) in the Tertiary reservoirs of the Zhongyuan Oilfield. Besides, 40Ar/36Ar values also have a positive effect on the oil-source correlation of oil reservoirs in ancient hidden mountains. According to the crust-mantle interchange information reflected by 3He/4He values, petroliferous provinces in China can be divided into three major tectonic regions. (1) The eastern active region: The crust-mantle volatile matter exchanges actively, and the 3He/4He values are mainly around 10-6, partly around 10-7. (2) The central stable region: The 3He/4He values are all around 10-8. (3) The western sub-stable region: The 3He/4He values are mainly around 10-8, and around 10-7 on the edges of the basins. Helium contents of some gas wells in China’s eastern petroliferous region reach the industrial abundance (He≈0.05%–0.1%), the 3He/4He values reach 10-6, and the equivalent values for the mantle-source components in helium gas can reach 30%–50%. As viewed from this, a new type of crust-mantle composite helium resources has been proposed. Geneses of some CO2 gas reservoirs in the east of China and some issues concerning mantle-source methane were discussed in the light of the helium and carbon isotopes of CO2 and CH4 in natural gases. In the discussion on helium isotopic characteristics of inclusions in the reservoirs, it was discovered that the 3He/4He values are close to those in natural gases. That is to say, this phenomenon is related to regional tectonism. The 3He/4He, CO2/3He and CH4/3He data were used to discuss the tectonic activities of fault zones in a certain number of regions in China.     

Sr, C and O isotope systematics in the Pucará basin, central Peru

A combined Sr, O and C isotope study has been carried out in the Pucará basin, central Peru, to compare local isotopic trends of the San Vicente and Shalipayco Zn-Pb Mississippi Valley-type (MVT) deposits with regional geochemical patterns of the sedimentary host basin. Gypsum, limestone and regional replacement dolomite yield ⁸⁷Sr/⁸⁶Sr ratios that fall within or slightly below the published range of seawater ⁸⁷Sr/⁸⁶Sr values for the Lower Jurassic and the Upper Triassic. Our data indicate that the Sr isotopic composition of seawater between the Hettangian and the Toarcian may extend to lower ⁸⁷Sr/⁸⁶Sr ratios than previously published values. An ⁸⁷Sr-enrichment is noted in (1) carbonate rocks from the lowermost part of the Pucará basin, and (2) different carbonate generations at the MVT deposits. This indicates that host rocks at MVT deposits and in the lower-most part of the carbonate sequence interacted with ⁸⁷Srenriched fluids. The fluids acquired their radiogenic nature by interaction with lithologies underlying the carbonate rocks of the Pucará basin. The San Ramón granite, similar Permo-Triassic intrusions and their clastic derivatives in the Mitu Group are likely sources of radiogenic ⁸⁷Sr. The Brazilian shield and its erosion products are an additional potential source of radiogenic ⁸⁷Sr. Volcanic rocks of the Mitu Group are not a significant source for radiogenic ⁸⁷Sr; however, molasse-type sedimentary rocks and volcaniclastic rocks cannot be ruled out as a possible source of radiogenic ⁸⁷Sr. The marked enrichment in ⁸⁷Sr of carbonates toward the lower part of the Pucará Group is accompanied by only a slight decrease in ¹⁸O values and essentially no change in ¹³C values, whereas replacement dolomite and sparry carbonates at the MVT deposits display a coherent trend of progressive ⁸⁷Sr-enrichment, and ¹⁸O- and ¹³C-depletion. The depletion in ¹⁸O in carbonates from the MVT deposits are likely related to a temperature increase, possibly coupled with a ¹⁸O-enrichment of the ore-forming fluids. Progressively lower ¹³C values throughout the paragenetic sequence at the MVT deposits are interpreted as a gradually more important contribution from organically derived carbon. Quantitative calculations show that a single fluid-rock interaction model satisfactorily reproduces the marked ⁸⁷Sr-enrichment and the slight decrease in ¹⁸O values in carbonate rocks from the lower part of the Pucará Group. By contrast, the isotopic covariation trends of the MVT deposits are better reproduced by a model combining fluid mixing and fluid-rock interaction. The modelled ore-bearing fluids have a range of compositions between a hot, saline, radiogenic brine that had interacted with lithologies underlying the Pucará sequence and cooler, dilute brines possibly representing local fluids within the Pucará sequence. The composition of the local fluids varies according to the nature of the lithologies present in the neighborhood of the different MVT deposits. The proportion of the radiogenic fluid in the modelled fluid mixtures interacting with the carbonate host rocks at the MVT deposits decreases as one moves up in the stratigraphic sequence of the Pucará Group.     

The Candelaria silver deposit,Nevada — preliminary sulphur,oxygen and hydrogen isotope geochemistry

The pre-Cenozoic geology at Candelaria, Nevada comprises four main lithologic units: the basement consists of Ordovician cherts of the Palmetto complex; this is overlain unconformably by Permo-Triassic marine clastic sediments (Diablo and Candelaria Formations); these are structurally overlain by a serpentinitehosted tectonic mélange (Pickhandle/Golconda allochthon); all these units are cut by three Mesozoic felsic dike systems. Bulk-mineable silver-base metal ores occur as stratabound sheets of vein stockwork/disseminated sulphide mineralisation within structurally favourable zones along the base of the Pickhandle allochthon (i.e. Pickhandle thrust and overlying ultramafics/mafics) and within the fissile, calcareous and phosphatic black shales at the base of the Candelaria Formation (lower Candelaria shear). The most prominent felsic dike system — a suite of Early Jurassic granodiorite porphyries — exhibits close spatial, alteration and geochemical associations with the silver mineralisation. Disseminated pyrites from the bulk-mineable ores exhibit a ³⁴S range from — 0.3 to + 12.1 (mean ³⁴S = +6.4 ± 3.5, 1, n = 17) and two sphalerites have ³⁴S of + 5.9 and + 8.7 These data support a felsic magmatic source for sulphur in the ores, consistent with their proximal position in relation to the porphyries. However, a minor contribution of sulphur from diagenetic pyrite in the host Candelaria sediments (mean ³⁴S = — 14.0) cannot be ruled out. Sulphur in late, localised barite veins ( ³⁴S = + 17.3 and + 17.7) probably originated from a sedimentary/seawater source, in the form of bedded barite within the Palmetto basement ( ³⁴S = + 18.9). Quartz veins from the ores have mean ¹⁸O = + 15.9 ± 0.8 (1, n = 10), which is consistent, over the best estimate temperature range of the mineralisation (360°–460°C), with deposition from ¹⁸O-enriched magmatic-hydrothermal fluids (calculated ¹⁸O fluid = + 9.4 to + 13.9). Such enrichment probably occurred through isotopic exchange with the basement cherts during fluid ascent from a source pluton. Whole rock data for a propylitised porphyry ( ¹⁸O = + 14.2, D = — 65) support a magmatic fluid source. However, D results for fluid inclusions from several vein samples (mean = — 108 ± 14, 1, n = 6) and for other dike and sediment whole rocks (mean = — 110 ± 13, 1, n = 5) reveal the influence of meteoric waters. The timing of meteoric fluid incursion is unresolved, but possibilities include late-mineralisation groundwater flooding during cooling of the Early Jurassic progenitor porphyry system and/or meteoric fluid circulation driven by Late Cretaceous plutonism.     

Changes in the HOAr isotope composition of clays during retrograde alteration

K-Ar ages of illite alteration associated with Middle Proterozoic Athabasca unconformity-type U deposits in Saskatchewan range from 414 to 1493 Ma. The K-Ar ages correlate with water contents and δD values such that illites with young K-Ar ages have δD values as low as −169 and water contents as high as 7.7 wt.% whereas illites with older ages have δD values near −70 and water contents near 4 wt.%. Water extracted at 400°C from illites with low δD values and high water contents has low δD and δ¹⁸O values similar to those of modern meteoric water suggesting that some of the illites associated with the original deposition of the ore underwent varying degrees of retrograde alteration. The alteration is initiated by hydration of sites in the interlayer region of the illite which results in the partial resetting of the K-Ar ages and introduction of excess structural water in the form of interlamellar water. The interlamellar water is enriched in ¹⁸O by about 7 per mil relative to the water that physically surrounded the clay particle. Further alteration decreases the δD value and increases the δ¹⁸O value of the illite by isotopic exchange between the mineral and the interlamellar water. Although the chemical compositions and XRD patterns of the altered illites indicate that no detectable smectite component is present in the samples, the isotopic results suggest that the altered illites may be an early precursor in the formation of mixed-layer illite/smectite by retrograde alteration of pure illite. The wide variation of δD values of chlorite and kaolinite from these U deposits is analogous to that of the illite suggesting that retrograde alteration of clays by meteoric water can be substantial. The general association of altered clays with areas containing the highest concentrations of U is probably related to localized permeability within the ore zone.     

Sulphur‐isotope study of the massive sulphide orebody at Woodlawn,New South Wales

³⁴S/³²S ratios have been measured in a suite of samples from the stratabound, volcanogenic massive sulphide deposit at Woodlawn, N.S.W. ³⁴S values for the sulphides vary as follows: in the ore horizon, pyrite +6.7 to +9.2%. (mean +8.1‰), sphalerite +5.2 to +8.6‰. (mean +6.9‰), chalcopyrite +6.4 to +7.0‰ (mean +6.7‰) and galena +2.8 to +5.5‰ (mean +4.4‰); in the vein mineralization, the host volcanics—pyrite +8.7 to +11.4%. (mean +9.8‰), sphalerite +7.8 to + 10.3‰ (mean +9.2‰), chalcopyrite; +8.8 to +10.1‰ (mean +9.2‰) and galena +6.9 to +7.2‰ (mean +7.1‰). Barite from the upper ore horizon levels has an isotopic composition of +30.0‰, consistent with its having originated from Silurian ocean sulphate. The general order of ³⁴S enrichment in the sulphides is pyrite > chalcopyrite ～ sphalerite > galena. Isotopic fractionations in the systems galena/sphalerite/pyrite and chalcopyrite/pyrite indicate an equilibration temperature of 275–300°C. This temperature is considered to represent that of sulphide deposition.     

Pb isotope variations in hydrogenetic Fe–Mn crusts from the Izu–Bonin fore-arc

Fe–Mn crusts were recovered from the western escarpment of the Bonin Ridge in the Izu–Bonin fore-arc region (dive site #824: 28.612°N, 141.803°E) at water depths of c. 2900 m using the Shinkai 6500 submersible during cruise YK 04–05. Major and trace element data and XRD mineralogy indicate that the crusts are hydrogenetic in origin. We present profiles of variations in Pb isotope composition measured in-situ by laser ablation MC-ICP-MS across two of the crusts. The isotopic variations are systematic and can be matched up between the two crusts, indicating similar growth rates. The crust Pb isotope composition rules out any local source for Pb from within the Izu–Bonin–Mariana arc system, either from hydrothermal activity or through leaching of volcanic detritus. Input of a globally well-mixed volcanic Pb component, either from aerosols or as an absorbed component on aeolian dust, has been proposed as a mechanism to explain the Pb isotope composition of Central Pacific deep water. However, the Izu–Bonin crusts are displaced to lower ²⁰⁶Pb/²⁰⁴Pb and higher ²⁰⁸Pb/²⁰⁴Pb, which requires an additional Pb source. One possibility is that as water is advected from the south, outboard of the Luzon–Ryukyu–Honshu arc system, it is progressively polluted by Pb derived by weathering and erosion of these young island arc volcanic systems. Using a constant Co-flux model, growth rates are estimated at ～ 7–13 mm/Ma, which would suggest that these crusts provide a record of changes in the composition of deep water in the Izu–Bonin fore-arc region of the western Pacific Ocean over the last 4–8 Ma. Over this interval, the main feature has been a progressive decrease in ²⁰⁷Pb/²⁰⁶Pb (0.843 to 0.839) and ²⁰⁸Pb/²⁰⁶Pb (2.088 to 2.080) with time. The interior parts have compositions similar to those of crusts from the Izu–Bonin fore-arc, while the rims have compositions similar to crusts from the central Western Pacific.