A record of changing redox conditions in the northern Peru Basin during the Late Quaternary deduced from Mn/Fe and growth rate variations in two diagenetic manganese nodules

Two diagenetic manganese nodules from the Peru Basin were investigated by thermal ionization mass spectrometry and high resolution alpha spectrometry for uranium and thorium. The TIMS concentrations for nodule 62KD (63KG) vary as follows: 0.12–1.01 ppb (0.06–0.59) ²³⁰Th, 0.51–1.98 ppm (0.43–1.40) ²³²Th, 0.13–0.80 ppb (0.09–0.49) ²³⁴U, and 1.95–13.47 ppm (1.66–8.24) ²³⁸U. Both nodules have average growth rates of 110 mm per million years. However, from the variations of excess ²³⁰Th with depth we estimate partial accumulation rates which range from 50 to 400 mm per million years. The δ²³⁴U dating method cannot be applied due to remobilization of U from the sediment and subsequent incorporation into the nodules' crystal lattice, reflected by decay corrected δ²³⁴U values far above the ocean water value. Sections of fast nodule growth are related to those layers having high Mn/Fe ratios (up to 200) and higher densities. As a possible explanation we develop a scenario that describes similar glacial/interglacial trends in both nodules as a record of regional changes of sediment and/or deep water chemistry.     

The flocculation of dissolved Fe,Mn, Al,Cu, Ni,Co and Cd during estuarine mixing

A laboratory experiment was carried out in which the flocculation products, formed from the mixing of filtered (0.4 μm) river water and seawater, were analysed. This study established that Fe, Mn, Al, Cu, Ni, Cd and Co have resolvable and well-defined estuarine chemistries. Copper, Ni, Mn and Co have salinity dependences of removal which are similar to those of dissolved Fe and humic acids. The amount of removal of the above trace metals increases between 0 and 15–18‰, after which little additional removal occurs. The extents of removal from river water are very different: Fe, 95%; Al, 20%; Cu, Ni, 40%; Co, 10%; Cd, 5% and Mn, 25–45%. The basic removal mechanism appears to be the estuarine flocculation of trace metals which exist, in part, in river water as colloids in association with colloidal humic acids and hydrous iron oxides. A qualitative model, based on this mechanism, supports the observations of this flocculation study.The results of this study give the most complete and consistent set of data presently available, from which to postulate the most important processes controlling the estuarine chemistry of trace metals. The generality of their behaviours still needs to be determined by future investigations.     

Coupling of early diagenetic processes and sedimentary dynamics in tropical shelf environments: the Gulf of Papua deltaic complex

Tropical mobile mud belts represent a major class of biogeochemical and diagenetic systems characterized by extensive and frequent physical reworking of fine-grained, organic-rich deposits underlying oxygenated waters. Large regions of the Gulf of Papua, Papua New Guinea deltaic complex are dominated by such conditions. A reworked mud belt lies within the inner shelf between 10 and 20 m depth on a sedimentary clinoform derived from coalescing deltas. Deposits across the topset are typically suboxic, nonsulfidic over the upper 0.5–1 m, and have low to moderate maximum pore water concentrations of dissolved Fe(II) and Mn(II) (100–200, but up to 800 μM). Sediments are reactive, with surficial ΣCO₂ production 0.1–0.3 mM d⁻¹ and benthic O₂ fluxes 23±15 mmol m⁻² d⁻¹ (upper 20 cm). The highest rates occur within inner topset deposits (10–20 m) and near the high accumulation rollover region of the topset–foreset beds (40–50 m). Lower rates are found inshore along intertidal channels—mangrove fringe and within scoured or exposed consolidated deposits of the middle topset region. Remineralization rate patterns are independent of relative dominance by terrestrial or marine carbon in sediments. Dissolved O₂ usually penetrates 2–5 mm into surface sediments when macrofaunal burrows are absent. More than 75% of the highly reactive sedimentary Fe(III) pool (350–400 μmol g⁻¹) is typically diagenetically reduced in the upper 0.5 m. Pore water can be measureably depleted at depths >0.5 m, but dissolved H₂S generally remains below detection over the upper 1–2 m. As in other deltaic topset regions, concentration gradients often indicate that compared to many marine deposits of similar sediment accumulation rates, relatively refractory C_org is supplied to the SO₄ reducing zone. Sedimentary C/S ratios are 4–6 within the suboxic topset regions but decrease to <3 in offshore foreset beds where sulfidic diagenesis dominates. Only 15–20% of the diagenetically reduced Fe(II) is pyritic and a maximum of 10–25% is carbonate, implying that most Fe(II) is associated with authigenic or lithogenic silicates or oxides. The dominance of suboxic, nonsulfidic diagenetic processes reflect coupling between delivery of oxide-rich terrestrial debris, remobilization and reoxidation of deposits, and repetitive entrainment/remineralization of both labile and refractory organics. Distinct sedimentary indicators of reactive, suboxic mobile mud belts within tropical climatic zones are: abundant total highly reactive Fe (ΣFeR )>300 μmol g⁻¹; most reactive Fe is diagenetically reduced (ΣFe(II)/ΣFeR0.7–0.8); the proportion of diagenetically reduced Fe present as pyrite is low (Py–Fe(II)<0.2); C/S 4–8; and C_org/particle surface area <0.4 (mg C m⁻²). These depositional environments must be most common in tropical climates during high sea stand.     

Sea-floor dynamic processes as the possible cause of correlations between paleoclimatic and paleomagnetic indices in deep-sea sedimentary cores

Recent publications showing correlations between the variation of intensity of magnetization(J) and paleomagnetic inclinationI on the one hand, and diverse paleoclimatic indices on the other, have been interpreted to represent direct cause and effect relationships between climate and geomagnetism.It is proposed that several sea-floor dynamic processes, which are climatically variable, are at least equally feasible causes of the observed correlations. Thus, for variation inJ, it is a simple matter to invoke variations in such factors as the magnetic particle size fraction below 50 microns, carbonate content, or laminar flow layer thickness, all of which can change with climate. For variation inI, climatically related variation of the velocity gradient in the laminar flow layer can be employed to explain the correlation.Prior to accepting the suggested geomagnetic control of climate as real, it is recommended that simple measurements of the temporal and geographic variation in fabric and composition of the deep-sea sediments involved should be carried out, as a check for the effect of bottom dynamic processes.     

Estimations of the uncertainty in timing the relationship between magnetospheric and solar wind processes

We present here a statistical study quantifying the errors associated with the most commonly used methods for propagating discontinuities in the interplanetary magnetic field (IMF) from an upstream monitor to the magnetosphere by the magnetospheric and ionospheric communities. The purpose of this paper is to show the quantified errors in the different techniques. Step changes in the IMF orientation were first identified at the WIND satellite. A total of 363 events were identified. Ninety percent of the events measured at WIND (330) were clearly observed in the IMP 8 data. Of those events, the time delay between the satellites could be determined to within 2 min in 288 events. Four propagation methods were used to estimate the time delay between WIND and IMP 8: (1) using only the X distance between the satellites; (2) assuming that the propagation front plane is in the plane of the Parker spiral; (3) using the IMF in the X–Y plane to estimate the propagation front plane; and (4) using the total IMF to determine the Z component of the propagation front plane. The average (Ē) and maximum (E_max) propagation error (in minutes) as a function of Y–Z distance (in R_e) were determined for each method. It is concluded that the average uncertainty in propagation is 7.5–8.5 min for off-axis distances of 30 R_e (which is the average WIND off-axis distance, and approximately the largest off-axis distance of IMP 8). For off-axis distances of 100 R_e (the largest off-axis distance of WIND), the uncertainties are 17.5–25 min, depending on the propagation method.     

Fe, Ni and Co variations in the metals of some antarctic chondrites

Nearly 4,000 Fe, Ni and Co analyses have been carried out on the metal phases of 12 Antarctic chondritic meteorites by means of the electron microprobe. H-group chondrites show relatively simple patterns of variation for these elements but L- and LL-group members show much more scatter in both Ni and Co concentrations. A single member of the CO3 group investigated shows some scatter in the concentrations and also much higher Co concentrations in the high-Ni (awaruite?) phase (1.25–2%) than in the coexisting kamacite (0.2–0.5%). Thus, analysis of the metal phases can provide not only a means of identifying the group to which a meteorite belongs, but also the possibility of distinguishing between individual chondrites from the same group.

The overall concentrations of Co in the metal particles in the different groups are considered to be related inversely to the abundance of metal grains in meteorites of these groups while the scatter is interpreted as reflecting characteristics inherited at the time of accretion. The absence of homogenisation of the concentrations of Fe, Ni and Co in the metal particles, even in so-called equilibrated chondrites, provides further evidence against the widely held notion that these meteorites have been involved in a high-temperature prograde metamorphism.     

水温分层型水库铁、锰垂直分布特征

贵阳市主要饮用水源地阿哈水库系水温分层型季节性缺氧水库,由于沉积物含高浓度Ｆｅ,Ｍｎ至使库水受到污染,经多年测定不同季节２０ｍ深垂直水柱结果表明,Ｆｅ,Ｍｎ分布随着季节变化,水库水温分层而变化,呈现明显的垂直分布规律,高浓度Ｆｅ,Ｍｎ主要出现在水温分层期水库中,下层,与库底缺氧,ＰＨ下降沉积物浓度Ｆｅ,Ｍｎ释放造成的二次污染等密切相关,从而为自来水厂实施优化分层取水和污染控制提供了依据。     

Hydrologic,geomorphic and climatic processes controlling willow establishment in a montane ecosystem

Willow communities dominate mid‐elevation riparian areas throughout the Rocky Mountains of North America. However, many willow stands are rapidly declining in aerial cover and individual plants in stature. A poor understanding of the processes that control willow establishment hinders identifying the causes of this decline. We analysed the processes that have facilitated or limited willow establishment over the last half of the 20th century on two large floodplains in Rocky Mountain National Park in Colorado by addressing two questions: (1) How does hydrologic regime control willow establishment on different fluvial landforms? (2) How might climate‐driven variations in hydrologic regime affect future willow establishment? We precisely aged willows on the three most common fluvial landforms, stream point bars, drained beaver ponds, and abandoned channels, and statistically related establishment dates to patterns of annual stream peak flow. The role of peak flow on willow establishment varied significantly by landform. Willow recruitment had occurred nearly every year on point bars. In former beaver complexes, most willows had established following dam breaches, whereas willows had established on abandoned channels for several years following channel avulsion. Establishment on point bars and abandoned channels was driven by peak flows of 2‐ to 5‐year return intervals, whereas in abandoned beaver ponds most establishment was associated with flow events of >5‐year return interval. Models of climate change suggest that temperatures will increase and precipitation seasonality will shift over the coming decades in the Rocky Mountains, leading to earlier spring runoff, lower summer and fall flows, decreased snowpack and decreased soil moisture. Such changes are likely to diminish opportunities for willow establishment. Copyright © 2005 John Wiley & Sons, Ltd.     

Deposition and fate of reactive Fe,Mn, P,and C in suspended particulate matter in the Bay of Biscay

Hydrographic structure of the water column, dissolved nutrient concentrations and the distribution of suspended particulate matter were recorded from CDT measurements and Niskin bottles sampling on the continental slope of the Bay of Biscay and on the axis of Capbreton canyon. Ascorbate extraction was applied here for the first time on marine suspended particles to determine the content of reactive Fe- and Mn-oxides, and P associated with Fe-oxides. Hydrographic structure of the south-eastern part of the Bay of Biscay did not change during the last three decades. Particulate organic carbon (POC) contents dropped strongly with depth, showing that organic matter mineralization was efficient in the water column. Organic matter mineralized in the water column had a Redfield N:P ratio. POC percent of particles collected at depth were higher during a bloom period, suggesting that some new organic matter reached the bottom. Contents of Fe and Mn extracted with the ascorbate leaching solution showed that suspended particles originated from the Gironde estuary, one of the major sources of particles in the Bay of Biscay. Intermediate and deeper nepheloid layers occurred in the Capbreton canyon. Particles of nepheloid layers were enriched in Mn- and Fe-oxides because they originated from resuspension of surface sediment.     

On the relationship between recent tectonic processes and mud volcanism by the example of Mt. Karabetov,Taman Peninsula

The results of studying the near-surface and deep structure of the mud volcano of Mt. Karabetov are presented. Based on direct observations in a specially dug trench and in the natural outcrops, together with the analysis of the structural morphological data, the structural kinematic characteristics are obtained for the fault zone associated with a mud volcano. The displacements of recent soil and overburden, as well as the topographic manifestations testify to the recent high level of mobility of the fault, whereas the natural structural parageneses suggest the primarily tectonic nature of the displacements, which is determined by the regional stress field.     

Experimental investigations into processes controlling stream and hyporheic temperatures,Fryxell Basin,Antarctica

Glacial meltwater streams in the McMurdo Dry Valleys, Antarctica exhibit daily cycles in temperature with maxima frequently reaching 10–15 °C, often 10 °C above air temperatures. Hydrologic and biogeochemical processes occurring in these streams and their hyporheic zones strongly influence the flux of water, solutes, and sediment to the ice-covered lakes on the valley bottoms. The purpose of this study was to identify the dominant processes controlling water temperature in these polar desert streams and to investigate in particular the role of hyporheic exchange. In order to do this, we analyzed stream temperature patterns on basin-wide, longitudinal, and reach scales. In the basin-wide study, we examined stream temperature monitoring data for seven streams in the Lake Fryxell Basin. For the longitudinal study, we measured temperatures at seven sites along a 5-km length of Von Guerard Stream.     

Kinetic partitioning of Co,Mn, Cs,Fe, Ag,Zn and Cd in fresh waters (Loire) mixed with brackish waters (Loire estuary): experimental and modelling approaches

To simulate the behavior of radionuclides along a salinity gradient, in vitro sorption and desorption kinetics of Co, Mn, Cs, Fe, Ag, Zn and Cd were studied in Loire river water and the macrotidal Loire estuarine water over two different seasons. Partitioning between the dissolved phase and suspended solids were followed up over 100 h after adding radioactive tracers to freshly collected freshwater (sorption stage); this stage was followed by desorption in fresh and estuarine waters. A kinetic model describing the interactions between trace metals and particles under a salinity gradient was developed and calibrated. Among parameters and/or processes that control the fate and behavior of contaminated particles during their transfer in estuarine systems, this study shows that the speciation of trace metals is controlled by: (i) the chemical water composition: for all the elements except for Fe, desorption increased with salinity; however, the amplitude of such an effect strongly depended on the element and/or on the composition of the particulate phase (and consequently on the season); (ii) the possibility for a given element to form (or not) stable surface particle moieties such as oxides or inner-sphere complexes; (iii) the distribution of a given element among different types of sites characterised by different binding forces that can lead (or not) to re-adsorption processes after mixing of contaminated particles with uncontaminated water.Our model enabled the quantification of the contribution and the characteristic time of reactions that took place over short and long periods on the global partitioning between particulate and dissolved phases during sorption and desorption and to determine the extent to which these reactions were modified by the salinity.     

Photosynthetic capability and Fe,Mn, Cu,and Zn contents in two Moraceae species under different phosphorus levels

The strong adaptability of Broussonetia papyrifera(L.) Vent. to low phosphorus(P) conditions can be attributed to the large amount of root-exuded organic acids and the high ef?ciency of P extraction. However,microelement contents are in?uenced by low-P stress, and their effects on the photosynthetic capability of B. papyrifera remain unknown. In this study, we investigated the effects of low-P treatment on net photosynthetic rate(P_N);chlorophyll a ?uorescence(ChlF) characteristics; and Fe,Mn, Cu, and Zn contents of B. papyrifera and Morus alba L. seedlings. Results show that B. papyrifera exhibited better photosynthetic capability under moderate P de?-ciency(0.125, 0.063, and 0.031 mmol/L P treatments),whereas the photosynthetic capability of M. alba decreased under moderate and severe P de?ciency(0.016 and0 mmol/L P treatments). Under moderate P de?ciency, the decrease in Cu and Zn contents in B. papyrifera was lower than that in M. alba. Under severe P de?ciency, a considerable decrease of photosynthetic capability in B. papyrifera and M. alba was associated with low Cu and Zn contents. The P N of the two Moraceae species exhibited a better correlation with Cu and Zn contents than with Fe or Mn content. P de?ciency could not only decrease cyclic photophorylation and photosynthetic ef?ciency, but could also affect the stability of thylakoid membrane structure and electron transport ef?ciency by in?uencing the contents of Cu or Zn, thereby affecting photosynthesis.     

Geochemical processes and origin of boron isotopes in geothermal water in the Yunnan-Tibet geothermal zone

Boron concentrations and isotope compositions have been measured for 93 water samples from the hot springs and drill-holes in the geothermal system in the Yunnan-Tibet Geothermal Belt(YTGB),China.Boron concentrations range from 0.036–472.4ppm,and theδ11B values range from -16.0‰to 13.1‰,indicating the non-marine origin for each geothermal system.We observed a clear binary mixing relationship between the B concentrations and B isotope compositions in Tibet geothermal area.This relationship can be well explained by two sources,i.e.,marine carbonate rocks and magmatic rocks,for the Tibet geothermal water.No evidence supports a mantle contribution to B.In addition,we found that the precipitation only plays a dilution role for B of geothermal waters.δ11B values for the precipitation across the southern Tibetan Plateau area range from -6.0‰ to -6.8‰at least.Due to data scarcity in Yunnan geothermal area,we observed possible different boron sources from the Tibet geothermal system.Comparing it with other geothermal systems in the world,we found that the samples from YTGB have the lowestδ11B values and the largest range of B concentration,which might be related to their special geological background.On the whole,the world geothermalδ11B-Cl/B relation suggests a mixing process between marine and non-marine sources.Additionally,we suggest that B source of B-enriched geothermal waters is mainly from B-enriched crustal country-rocks,instead of mantle.     

Sedimentary profiles of Fe, Mn, V, Cr, As and Mo as indicators of benthic redox conditions in Baldeggersee

Concentration profiles of Mg, K, La, Fe, Mn, V, Cr, As and Mo were determined in samples from a freeze core taken at the deepest site of Baldeggersee in 1993. The special coring technique allowed an exact dating of the sediment samples and an annual resolution of the profiles. Long term changes in benthic redox conditions produce diagnostic trends in several metal profiles. Fe, As and Mn enrichments trace the onset of anoxia at the deepest site of the lake. High values of Mo concentrations and Cr/V ratios indicate periods of stable anoxic conditions in a meromictic hypolimnion. A comparison of oxygen time series with metal profiles between 1950 and 1990 indicates that Mn reacts sensitively to large seasonal variations of deep-water oxygen concentrations.     

Equilibrium Fe isotope fractionation between inorganic aqueous Fe(III) and the siderophore complex, Fe(III)-desferrioxamine B

In oxic oceans, most of the dissolved iron (Fe) exists as complexes with siderophore-like, strongly coordinating organic ligands. Thus, the isotope composition of the little amount of free inorganic Fe that is available for precipitation and preservation in the geological record may largely be controlled by isotope fractionation between the free and complexed iron. We have determined the equilibrium Fe isotope fractionation induced by organic ligand activity in experiments with solutions having co-existing inorganic Fe(III) species and siderophore complexes, Fe-desferrioxamine B (at pH 2). The two differently complexed Fe(III) pools were separated by addition of Na₂CO₃, which led to immediate precipitation of the inorganic Fe without causing significant dissociation of Fe-desferrioxamine complexes. Experiments using enriched ⁵⁷Fe tracer showed that isotopic equilibration between the ⁵⁷Fe-labelled inorganic species and the isotopically “normal” siderophore-bound Fe was rapid during the first few seconds and then became slower. Consequently, the data fitted poorly to first and second order reaction equations. However, with a two-stage reaction, the data fit perfectly with a first order equation for the slower stage, indicating that approximately 40% re-equilibration may take place during the separation of the two pools. To further test if the induced precipitation leads to experimental artefacts, the fractionation during precipitation of inorganic Fe was determined. Assuming a Rayleigh-type fractionation during precipitation, this experiment yielded an isotope fractionation factor of ⁵⁶Fe_{solution-solid} = 1.00027. Calculations based on these results indicate that isotopic re-equilibration is unlikely to significantly affect our determined equilibrium Fe isotope fractionation between inorganically and organically complexed Fe. To determine the equilibrium Fe isotope fractionation between inorganically and organically bound Fe(III), experiments with variable proportions of inorganic Fe were carried out at 25 °C. Irrespective of the proportion of inorganic Fe, equilibrium fractionation factors were within experimental uncertainty, yielding an average fractionation factor, Δ⁵⁶Fe_DFOB-inorg of 0.60 ± 0.15‰. The results indicate that equilibrium Fe isotope fractionation induced by strongly coordinating organic ligands may fractionate Fe isotopes in nature. The fractionation is likely to be important in oxic, Fe(III)-bearing environments, such as soils and rivers, and may, for example, largely control the Fe isotope composition of marine Fe–Mn crusts.     

吉林省龙岗火山岩区早更新世粗面玄武岩地球化学特征及构造意义

中国是全球晚新生代火山发育国家之一,也是西环太平洋活动大陆边缘火山活动带重要组成部分.在我国东北地区发育着数座晚新生代喷发过的活火山(如五大连池老黑山、火烧山火山、金龙顶子火山等)或具备喷发能力的休眠火山(如云南腾冲火山、长白山天池火山等)( Hickey,1982;Davies et al,1992;刘若新,1992...     

Fractionation characteristics of rare earth elements(REEs) linked with secondary Fe,Mn, and Al minerals in soils

Soil secondary minerals are important scavengers of rare earth elements(REEs) in soils and thus affect geochemical behavior and occurrence of REEs. The fractionation of REEs is a common geochemical phenomenon in soils but has received little attention, especially fractionation induced by secondary minerals. In this study, REEs(La to Lu and Y) associated with soil-abundant secondary minerals Fe-, Al-, and Mn-oxides in 196 soil samples were investigated to explore the fractionation and anomalies of REEs related to the minerals. The results show right-inclined chondrite-normalized REE patterns for La–Lu in soils subjected to total soil digestion and partial soil extraction. Light REEs(LREEs) enrichment features were negatively correlated with a Eu anomaly and positively correlated with a Ce anomaly. The fractionation between LREEs and heavy REEs(HREEs) was attributed to the high adsorption affinity of LREEs to secondary minerals and the preferred activation/leaching of HREEs.The substantial fractions of REEs in soils extracted byoxalate and Dithionite-Citrate-Bicarbonate buffer solutions were labile(10 %–30 %), which were similar to the mass fraction of Fe(10 %–20 %). Furthermore, Eu was found to be more mobile than the other REEs in the soils, whereas Ce was less mobile. These results add to our understanding of the distribution and geochemical behavior of REEs in soils, and also help to deduce the conditions of soil formation from REE fractionation.