Metalliferous sediments from DSDP Leg 92: The East Pacific Rise transect

The carbonate-free metalliferous fraction of thirty-nine sediment samples from four DSDP Leg 92 sites has been analyzed for 12 elements, and a subset of 16 samples analyzed for Pb isotopic composition. The main geochemical features of this component are as follows: i) very high concentrations of Fe and Mn, typically 25–39% and 5–14%, respectively; ii) Al and Ca contents generally less than 2% and 5%, respectively; iii) high Cu (1000–2000 ppm), and Zn and Ni (500–1000 ppm) values; and iv) Co and Pb concentrations of 100–250 ppm. In terms of element partitioning within the metalliferous fraction, amorphous to poorly crystallized oxide-oxyhydroxides removed by the second leach carry virtually all of the Mn, and about 90% of the Ca, Sr and Ni. The well-crystallized goethite-rich material removed by the third leach carries the majority of Fe, Cu, and Pb. These relations hold for sediments as young as ~ 1–2 Ma, indicating early partitioning of hydrothermal Fe and Mn into separate phases.Calculated mass accumulation rates (MAR) for Fe, Mn, Cu, Pb, Zn and Ni in the bulk sediment show the same overall trends at three of the sites, with greatest MAR values near the basement, and a general decrease in MAR values towards the tops of the holes (for sediments deposited above the lysocline). These relations strongly support the concept of a declining hydrothermal contribution of these elements away from a ridge axis. Nevertheless, MAR values for these metals up to ~200 km from the ridge axis are orders of magnitude higher than on abyssal seafloor plains where there is no hydrothermal influence. Mn/Fe ratios throughout the sediment column at two sites indicate that the composition of the hydrothermal precipitates changed during transport through seawater, becoming significantly depleted in Mn beyond 2̃00–300 km from the axis, but maintaining roughly the same proportion of Fe.Most of the Pb isotope data for the Leg 92 metalliferous sediments form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts toward the field for Mn nodules. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb derived from basaltic and seawater end-member sources. The least radiogenic sediments reflect the average Pb isotope composition of discharging hydrothermal solutions and ocean-ridge basalt at the EPR over the ≈4–8 Ma B.P. interval. Pb in sediments deposited up to 250 km from the axis can be almost entirely of basaltic-hydrothermal origin. Lateral transport of some basaltic Pb by ocean currents appears to extend to distances of at least 1000 km west of the East Pacific Rise.     

Do Archean chemical sediments record ancient seawater rare earth element patterns?

Rare earth elements (REE) concentrations of Archean and Proterozoic chemical sediments are commonly used as proxies to study secular trends in the geochemistry of Precambrian seawater. In addition, similarities in the REE signatures of Archean chemical sediments and modern seawater have led researchers to argue that some Archean rocks originated as biochemical precipitates (i.e., microbial carbonates) in shallow marine (e.g., peritidal) environments. However, terrestrial waters, including river water and groundwater, also commonly exhibit REE fractionation patterns that resemble modern seawater. Here, we present the seawater-like REE data for groundwaters from central México as additional evidence that these patterns are not unique to the marine environment. The shale-normalized REE patterns of the groundwaters are compared to those of modern seawater (open ocean and nearshore), Holocene reefal microbial carbonates and corals, and Archean chemical sediments using statistical means (i.e., ANOVA and Wilcoxon analyses) in order to quantify the similarities and/or differences in the REE patterns. Shale-normalized (SN) Ce anomalies and measures of REE fractionation [i.e., (La/Yb)_SN, (Pr/Yb)_SN, (Nd/Yb)_SN, and (Gd/Yb)_SN] of the central México groundwater samples are statistically indistinguishable from those of modern seawater. Moreover, except for differences in the Ce anomalies, which are lacking in Archean chemical sediments, the REE patterns of the central México groundwaters are also statistically similar to REE patterns of Archean chemical sediments, especially those of the 3.45 Ga Strelley Pool Chert. Consequently, we suggest that without additional information, it may be premature to unequivocally conclude that Archean chemical sediments record REE signatures of an Archean ocean.     

Co-diagenesis of iron and phosphorus in hydrothermal sediments from the southern East Pacific Rise: Implications for the evaluation of paleoseawater phosphate concentrations

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ∼19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ∼12 m. Molar P/Fe ratios are then relatively constant to a depth of ∼35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.     

Trace elements geochemistry and petrogenesis of basalt from the southern part of the East Pacific Rise

Trace element geochemistry of basalt samples collected from 6°S-24°S of the southern EPR, representing a super-fast spreading axis is discussed. Trace element data classify these basalts into Normal and Transitional types of MORB, however, LREE enrichment is also observed in few of them. Chondrite normalized REE data plots show highly fractionated nature of these lavas, suggesting their derivation from the primitive mantle source. Petrogenetic modeling of the data suggests variation in the solidus pressure (14–20 kb.) and temperature (1316–1425°C), where 15 to 20% partial melting of the mantle is accountable for the generation of the melt. The pressure and temperature conditions at the beginning of the mantle melting were high along higher latitudes (24°S of EPR), but it gradually lowered down in the lower latitudinal areas (6°S of EPR), supporting for the presence of passively rising upper mantle beneath the Southern EPR.     

Juan de Fuca洋脊Endeavour段热液硫化物稀土元素地球化学特征

用 ICP-MS对取自 Juan de Fuca洋脊 Endeavour段 5块热液硫化物样品的 13个分析样进行了稀土元素(REE)测试.结果显示该区硫化物样品的 REE含量较低(0.35～ 14.8 μ g/g),所有样品的 REE球粒陨石标准化分布模式均表现出 Eu正异常和 LREE富集的特征,表明硫化物中的 REE来自热液.不同喷口硫化物的 REE含量变化较大,同一块状硫化物不同部位的含量也有较大差异,主要是由于硫化物形成过程中,热液和海水的混合不均一性以及不同矿物沉淀和 (或 )溶解的结果.硫化物 REE的分布特征主要受热液的影响,烟囱内外层 Eu正异常的变化主要受矿物组成和物理化学条件的控制.     

Rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments

Analyses have been made of REE contents of a well-characterized suite of deep-sea (> 4000 m.) principally todorokite-bearing ferromanganese nodules and associated sediments from the Pacific Ocean. REE in nodules and their sediments are closely related: nodules with the largest positive Ce anomalies are found on sediments with the smallest negative Ce anomalies; in contrast, nodules with the highest contents of other rare earths (3 + REE) are found on sediments with the lowest 3 + REE contents and vice versa. ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratios in the nodules (～0.51244) point to an original seawater source but an identical ratio for sediments in combination with the REE patterns suggests that diagenetic reactions may transfer elements into the nodules. Analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to REE contents of nodules and sediments is negligible. Inter-element relationships and leaching tests suggest that REE contents are controlled by a P-rich phase with a REE pattern similar to that for biogenous apatite and an Fe-rich phase with a pattern the mirror image of that for sea water. It is proposed that 3 + REE concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate. Processes which favour the enrichment of transition metals in equatorial Pacific nodules favour the depletion of 3 + REE in nodules and enrichment of 3 + REE in associated sediments. In contrast, Ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions.     

Ligand extraction of rare earth elements from aquifer sediments: Implications for rare earth element complexation with organic matter in natural waters

The ability of organic matter as well as carbonate ions to extract rare earth elements (REEs) from sandy sediments of a Coastal Plain aquifer was investigated for unpurified organic matter from different sources (i.e., Mississippi River natural organic matter, Aldrich humic acid, Nordic aquatic fulvic acid, Suwannee River fulvic acid, and Suwannee River natural organic matter) and for extraction solutions containing weak (i.e., CH₃COO⁻) or strong (i.e., ) ligands. The experimental results indicate that, in the absence of strong REE complexing ligands in solution, the amount of REEs released from the sand is small and the fractionation pattern of the released REEs appears to be controlled by the surface stability constants for REE sorption with Fe(III) oxides/oxyhydroxides. In the presence of strong solution complexing ligands, however, the amount and the fractionation pattern of the released REEs reflect the strength and variation of the stability constants of the dominant aqueous REE species across the REE series. The varying amount of REEs extracted by the different organic matter employed in the experiments indicates that organic matter from different sources has different complexing capacity for REEs. However, the fractionation pattern of REEs extracted by the various organic matter used in our experiments is remarkable consistent, being independent of the source and the concentration of organic matter used, as well as solution pH. Because natural aquifer sand and unpurified organic matter were used in our experiments, our experimental conditions are more broadly similar to natural systems than many previous laboratory experiments of REE-humic complexation that employed purified humic substances. Our results suggest that the REE loading effect on REE-humic complexation is negligible in natural waters as more abundant metal cations (e.g., Fe, Al) out-compete REEs for strong binding sites on organic matter. More specifically, our results indicate that REE complexation with organic matter in natural waters is dominated by REE binding to weak sites on dissolved organic matter, which subsequently leads to a middle REE (MREE: Sm-Ho)-enriched fractionation pattern. The experiments also indicate that carbonate ions may effectively compete with fulvic acid in binding with dissolved REEs, but cannot out compete humic acids for REEs. Therefore, in natural waters where low molecular weight (LMW) dissolved organic carbon (DOC) is the predominant form of DOC (e.g., lower Mississippi River water), REEs occur as “truly” dissolved species by complexing with carbonate ions as well as FA, resulting in heavy REE (HREE: Er-Lu)-enriched shale-normalized fractionation patterns. Whereas, in natural terrestrial waters where REE speciation is dominated by organic complexes with high molecular weight DOC (e.g., “colloidal” HA), only MREE-enriched fractionation patterns will be observed because the more abundant, weak sites preferentially complex MREEs relative to HREEs and light REEs (LREEs: La-Nd).     

Chemistry of submarine hydrothermal solutions at 21 °N,East Pacific Rise

The three hydrothermal fields at 21°N latitude, East Pacific Rise, were resampled and an additional one was discovered. Maximum fluid temperatures observed were within a few degrees of 350°C and these waters had concentrations of Mg and sulfate indistinguishable from zero. One field, NGS, which had active 350°C springs in 1979, was inactive when first located in 1981. However, when a chimney was broken open during sampling, water issued at 273°C and continued to flow for at least five days. The chemical composition strongly suggests that these waters cooled conductively from 350°C in the sealed conduit.The major ion data are consistent with the estimates based on extrapolation of the original measurements made on the hot springs from the Galapagos Spreading Center (Edmondet al., 1979a). The fluids have a pH of 3.5 and the sulfide-forming element concentrations show significant inter-field variations. Fe levels range from 0.8 to 2.4 mmoles/kg; the ratio Fe:Mn varies from 0.9 to 2.9 similar to metalliferous sediments on the ridge flanks, but much higher than observed at Galapagos (where sub-surface precipitation of iron sulfides occurs) indicating that the overwhelming proportion of the mass flux from hydrothermal systems occurs at high temperatures. Zn ranges from 40 to 106 μmoles/kg with Cu being substantially lower. Since the ratio of these elements in tholeiites is about unity, there is strong net preferential mobilization of Zn. Lead ranges from 183 to 359 nmoles/kg. Nickel and Be are highly immobile relative to the other trace elements. The abundance of H₂S is about three times that of the total sulfide-forming cations. These data demonstrate that acid solutions at elevated temperatures can transport substantial amounts of ore-forming elements in the presence of large excesses of sulfide.     

河南周庵铂族-铜镍矿床的稀土和铂族元素地球化学特征: 热液成矿的证据

河南周庵超基性岩体蕴含大型Ni-Cu-(PGE)硫化物矿床,矿化带位于超基性岩体边缘与围岩的接触带.周庵超基性岩体轻稀土富集,其La/Sm_N比值为1.3～4.7,Sm/Yb_N比值为1.9～4.4,显示一定程度的LREE/HREE分异.原始地幔标准化的微量元素配分型显示弱的负Nb异常.岩体的M含量为70×10~(-60～2120×10~(-6),Cu含量为15×10~(-6)～1056×10~(-6);矿石的Ni含量为2592×10~(-6)～6549×10~(-6),Cu含量为1147×10~(-6)～3239×10`(-6).矿石的Ni/Cu比值(2.0～2.3)低于岩石样品(5-83).强蚀变矿化样品的PGE元素含量高于弱蚀变样品约一个数量级,所有样品的Pd/Ir和Pt/Ir比值高,Pd/Ir=1.4～21,Pt/Ir=2.4～22,表明PPGE相对IPGE富集.上述特征显示周庵岩体是构造侵位的地幔岩,岩体与围岩发生了较强烈的物质交换,含水流体交代作用导致了岩体-围岩物质交换和岩体边缘矿化.     

The rare earth element geochemistry of granite,gneiss, and migmatite from the Western Metamorphic Belt of South-eastern Australia

Four muscovite-biotite granites from the Western Metamorphic Belt of South-eastern Australia have rare earth element patterns characterized by: (i) light rare earth element enrichment; (ii) slight Eu depletion; (iii) varying degrees of heavy rare earth element depletion. The rare earth element and major element chemistry of three of these muscovite-biotite granites (the Koetong, Lockharts and Yabba Granites) can be approximated very closely by a model involving 20% partial melting of an ultrametamorphosed pelitic sediment and contamination of this minimum melt by the residual material left after melting, in the ratio 60% melt: 40% residue. Granitoids can be very largely solid material at the time of emplacement.The other muscovite-biotite granite studied (the Hawksview Granite) has major and trace element characteristics which distinguish if from the other three granitoids and these differences are attributed to variations in source material at the site of melt generation.The rare earth element and major element chemistry of a garnet-cordierite gneiss from the Western Metamorphic Belt can be modelled assuming 5% partial melting of a pelitic metamorphic rock and contamination of the minimum melt by the residue in the ratio 30% melt: 70% residue.Separated granitic and biotitic portions of a migmatite from the Western Metamorphic Belt have rare earth element characteristics which are inconsistent with a simple partial-melting model, but it is suggested that re-equilibration following, or during, separation of the vein material could obscure the process by which the vein of the migmatite developed. It is however certain that the vein developed in situ from a pelitic meta-sediment leaving the biotite rich selvage, without the introduction of material from an external source.Leucogranites which crop out to the east of the Western Metamorphic Belt are high level intrusions of highly fractionated granitic melt. Their Sr isotopic characteristics and features of their major and trace element chemistry suggest that they derive from an igneous source and are not directly related to the granites and gneisses to the west.     

The trace element geochemistry of clinopyroxenes from pyroxenites in the Lewisian of NW Scotland: insights into light rare earth element mobility during granulite facies metamorphism

Clinopyroxenes from layered pyroxenites and from pyroxenite pods in felsic gneisses of the Lewisian granulite complex, NW Scotland, have distinctive chemistries suggestive of different origins. Clinopyroxenes in the layered pyroxenites crystallised from mafic melts in a magma chamber located in the middle to shallow crust, whereas clinopyroxenes in pods in the felsic gneisses crystallised from the tonalitic protolith to the felsic gneisses. In detail clinopyroxenes in the layered pyroxenites are variably enriched in the light REE. Inversion modelling shows that this is not a primary feature inherited from their parent magmas. Rather selective light rare earth element enrichment took place through reaction with a felsic melt generated by the localised partial melting of the hornblende pyroxenites during granulite facies metamorphism. Published isotopic evidence suggests that the light REE mobilisation took place at ca 2.7 Ga, about 200 Ma after the time of crust formation. This observation provides an explanation for the scattered pattern of whole-rock isochron ages from the Lewsian granulites.     

Sources of stream sediments in the granulite terrain of the Walawe Ganga Basin,Sri Lanka,indicated by rare earth element geochemistry

Thirty-eight samples of stream sediments draining high-grade metamorphic rocks in the Walawe Ganga (river) Basin, Sri Lanka, were analysed for their REE contents, together with samples of metamorphic suites from the source region. The metamorphic rocks are enriched in light REE (LREE) compared to heavy REE (HREE) and are characterised by high La/Lu ratios and negative Eu anomalies. The chondrite-normalised patterns for these granulite-grade rocks are similar to that of the average post-Archaean upper crust, but they are slightly enriched with La and Ce. The REE contents of the <63-μm fraction of the stream sediments are similar to the probable source rocks, but the other grain size fractions show more enriched patterns. The <63-μm stream sediments fraction contains lower total REE, more pronouncd negative Eu anomalies, higher Eu_N/Sm_N and lower La _N/Lu_N ratios relative to other fractions. The lower La _N/Lu_N ratio is related to the depletion of heavy minerals in the <63-μm fraction. The 63–125-μm and 125–177-μm grain size fractions of sediments are particularly enriched in LREE (average ΣLREE=2990 μg/g and 3410 μg/g, respectively). The total HREE contents are surprisingly uniform in all size fractions. However, the REE contents in the Walawe Ganga sediments are not comparable with those of the granulite-grade rocks from the source region of the sediments. The enrichment of REE is accounted for by the presence of REE containing accessory mineral phases such as zircon, monazite, apatite and garnet. These minerals are derived from an unknown source, presumably from scattered bodies of granitic pegmatites.     

Kiglapait geochemistry VII: Yttrium and the rare earth elements

Based on 51 wholerock analyses by XRF and summation over the layered group, the Kiglapait Intrusion contains 4.7_?1.6^+1.2 ppm Y, which resides principally in augite and apatite. Using liquid compositions calculated by summation, the partition coefficient D^AUG/L_Y is 0.95 ± 0.12 from 84 to 97 PCS (percent solidified) and 1.5 ± 0.4 above 97 PCS. For feldspar, the most likely value for D is 0.028 ± 0.02 (N = 6).REE analyses for 13 whole rocks were interpreted with the aid of yttrium models to yield trends for wholerocks and liquids vs PCS. Summations over the rocks of the layered group gave La = 2.5, Ce = 5.8, Nd = 3.9, Sm = 1.0, Eu = 0.8, Tb = 0.17, Yb = 0.37, and Lu = 0.06 ppm, with 2 s.d. errors near ± 30%. All these elements are highly incompatible until the arrival of augite, which affects chiefly the HREE, and apatite, which affects all (but more strongly, the LREE). The net result is that after apatite arrival at 94 PCS, the liquid compositions are nearly constant, hence D^WR/L_REE ≈ 1.0. These results are compatible with the mineralogy of the intrusion and the estimated partition coefficients for feldspar, olivine, augite, apatite, and Fe-Ti oxide minerals. For pre-apatite liquids, D^FSP/L_REE vary regularly with the normative di content of the liquid and change by an order of magnitude, hence the bulk liquid composition must be considered in any attempt to invert the compositions of feldspars to parent liquids.The Eu anomaly at first decreases in Kiglapait liquids due to plagioclase fractionation, but then increases due to removal of augite and apatite with negative Eu anomalies. The features dominantly responsible for Eu partitioning are liquid structure and, for monoclinic ternary feldspars, crystal structure. The former is best monitored by the augite or diopside content of the liquid and the latter, by the K content of the feldspar.The chondrite-normalized REE pattern for the intrusion has La_N = 7.4, Lu_N = 1.6, (Ce/Yb)_N = 3.6, and Eu/Eu* = 2.4, indicating its feldspar-rich nature. The chilled margin of the nearby Hettasch Intrusion has a similar but more evolved pattern, corresponding roughly to the Kiglapait liquid at 70 PCS. As with other data, those for the REE suggest source differences for the two intrusions rather than a relationship due to fractionation.     

Origin of native sulfur ball from the Kueishantao hydrothermal field offshore northeast Taiwan: Evidence from trace and rare earth element composition

We first report the trace and rare earth element compositions of native sulfur ball with sulfur contents varying from 97.08 wt.% to 99.85 wt.% from the Kueishantao hydrothermal field, off NE Taiwan. We then discuss the sources of trace and rare earth elements incorporated into the native sulfur ball during formation. Comparison of our results with native sulfur from crater lakes and other volcanic areas shows the sulfur content of native sulfur ball from the Kueishantao hydrothermal field is very high, and that the rare earth element (REE) and trace element constituents of the native sulfur balls are very low (∑REE < 35 ppb). In the native sulfur ball, V, Cr, Co, Ni, Nb, Rb, Cs, Ba, Pb, Th, U, Al, Ti and REE are mostly derived from andesite; Mg, K and Mn are mostly derived from seawater; and Fe, Cu, Zn and Ni are partly derived from magma. Based on the sulfur contents, trace and rare earth element compositions, and local environment, we suggest that the growth of the native sulfur ball is significantly slower than that of native sulfur chimneys, which results in the relatively higher contents of trace and rare earth element contents in the native sulfur ball than in the native sulfur chimneys from the Kueishantao hydrothermal field. Finally, we suggest a “glue pudding” growth model for understanding the origin of the native sulfur ball in the Kueishantao hydrothermal field, whereby the native sulfur ball forms from a mixture of oxygenated seawater and acidic, low-temperature hydrothermal fluid with H₂S and SO₂ gases, and is subsequently shaped by tidal and/or bottom currents.     

稀土元素在岩浆和水热系统的实验岩石学和地球化学研究进展

稀土元素对绿色科技的发展具有至关重要的作用,随着世界范围内新兴技术的发展进程对稀土的需求日益提高,稀土矿床成矿机理的研究已经成为目前国际地学的研究热点。稀土元素分配行为的高温高压实验能够为研究稀土在岩浆和水热系统中的迁移、分异和沉淀机制提供有效制约,为了解稀土元素地球化学行为和稀土成矿作用提供重要的理论基础。本文总结了近年来关于稀土元素在岩浆-热液体系中分配行为的高温高压实验研究进展,其中包括部分熔融作用稀土的分配行为,液态不混熔过程中稀土在共轭熔体相之间的分配系数,分离结晶作用过程中稀土在结晶矿物相与残余熔体相之间的分配系数,岩浆演化后期稀土在熔体和分异流体相之间的分配行为,以及稀土在热液流体中的迁移、分异和沉淀机制的相关研究。基于目前的实验研究结果,本文提出了稀土实验地球化学研究中依旧存在的一些问题：部分熔融作用对于成矿物质组成的影响,碳酸盐熔体和硅酸盐熔体液态不混熔对于碳酸岩稀土成矿作用的影响,岩浆晚期演化的热液流体对于稀土成矿作用的影响,稀土元素在液态不混熔、分离结晶和热液交代过程中的分异和富集机制等,并对未来需要继续完善和拓展的方向提出了展望。

     

Hydrothermal venting and basin evolution (Devonian,South China): Constraints from rare earth element geochemistry of chert

This paper presents rare earth element (REE) geochemistry of siliceous deposits from which hydrothermal activity and basin evolution are elucidated, in the Late Devonian, in the Yangshuo basin, South China, where siliceous deposits widely occurred as nodular chert in the deep-water limestones and bedded chert interbeded with tuffaceous chert in the early Late Devonian. Both nodular and bedded cherts are characterized by very low La abundances (avg. 2.07 and 2.49 ppm, respectively), intermediate negative Ce anomalies (Ce/Ce*: avg. 0. 69 and 0.61), slight to intermediate positive Eu anomalies (Eu/Eu*: avg. 1.33 and 1.57), and low to intermediate shale-normalized La_n/Yb_n values (avg. 0.86 and 0.52) and intermediate La_n/Ce_n values (avg. 1.61 and 1.72). These suggest both nodular and bedded cherts formed in the open marine basin of South China, rather than in the intracontinental rift basin as previously assumed, with involvement both with seawaters as indicated by intermediate negative Ce anomalies and generally LREE-depleted patterns, and hydrothermal vent fluids as indicated by convex, less LREE-depleted patterns with apparent positive Eu anomalies. In comparison with nodular and bedded chert, the tuffaceous chert has the highest La abundances (avg. 17.11 ppm), similar ranges of Ce anomalies (avg. 0.63) and La_n/Ce_n values (avg. 1.77), but lower La_n/Yb_n values (avg. 0.48) and no apparent positive Eu anomalies (avg. 0.97). This suggests that the tuffaceous fallouts were also significantly modified by the hydrothermal fluid and seawater. Rapid spatial variations of Eu/Eu* values and degree of LREE-depletions in the studied basin are recognized, characterizing a spatially differential hydothermal activity that is not well discriminated by major element features. Such a difference in hydrothermal activity is interpreted as having been related to the intensity and depth of syndepositional tectonic activity, reconciling the structural pattern unraveled by stratigraphic packages.     

黄河、长江与韩国Keum、Yeongsan江沉积物常量元素地球化学特征

运用同样的样品采集和测试方法比较分析了我国的长江和黄河以及韩国的Keum和Yeongsan江的常量元素地球化学特征。韩国河流沉积物中Ca及碳酸盐含量显著低于长江和黄河,而其他元素含量则在二者之间;黄河沉积物以总无机碳(TIC)、Na和Ca含量高为特征,而长江沉积物则显著富集Ti和P。Keum和Yeongsan江沉积物中P、Ca、Fe和Mg在酸溶相中比例可达30％～66％,而K、Al和Ti则富集在残渣相中。韩国河流沉积物极低的Ca含量同流域缺乏碳酸盐源岩密切相关,其沉积物主要由侏罗一晚白垩纪的花岗岩经过中等程度的化学风化而成。虽然Ca在中韩河流沉积物之间含量差异显著,但必须谨慎运用全钙含量来识别海区物源。而沉积物中非碳酸盐态钙(Ca^*)及相应的K／Ca^*和Al／Ca^*比更适合用来示踪黄河及Keum和Yeongsan江沉积物;Ti则可以用来区分长江与其他河流沉积物。