Kinetic fractionation of Fe isotopes during transport through a porous quartz-sand column

Sorption and desorption processes are an important part of biological and geochemical metallic isotope cycles. Here, we address the dynamic aspects of metallic isotopic fractionation in a theoretical and experimental study of Fe sorption and desorption during the transport of aqueous Fe(III) through a quartz-sand matrix. Transport equations describing the behavior of sorbing isotopic species in a water saturated homogeneous porous medium are presented; isotopic fractionation of the system (Δ_{sorbedmetal-soln}) being defined in terms of two parameters: (i) an equilibrium fractionation factor, α_e; and (ii) a kinetic sorption factor, α₁. These equations are applied in a numerical model that simulates the sorption-desorption of Fe isotopes during injection of a Fe(III) solution pulse into a quartz matrix at pH 0-2 and explores the effects of the kinetic and equilibrium parameters on the Fe-isotope evolution of porewater. The kinetic transport theory is applied to a series of experiments in which pulses of Na and Fe(III) chloride solutions were injected into a porous sand grain column. Fractionation factors of α_e = 1.0003 ± 0.0001 and α₁ = 0.9997 ± 0.0004 yielded the best fit between the transport model and the Fe concentration and δ⁵⁶Fe data. The equilibrium fractionation (Δ⁵⁶Fe_{sorbedFe-soln}) of 0.3‰ is comparable with values deduced for adsorption of metallic cations on iron and manganese oxide surfaces and suggests that sandstone aquifers will fractionate metallic isotopes during sorption-desorption reactions. The ability of the equilibrium fractionation factor to describe a natural system, however, depends on the proximity to equilibrium, which is determined by the relative time scales of mass transfer and chemical reaction; low fluid transport rates should produce a system that is less dependent on kinetic effects. The results of this study are applicable to Fe-isotope fractionation in clastic sediments formed in highly acidic conditions; such conditions may have existed on Mars where acidic oxidizing ground and surface waters may have been responsible for clastic sedimentation and metallic element transport.     

The abundance and diversity of larval and juvenile fish in a tropical estuary

The larval and juvenile fish of the Cayenne river estuary (French Guiana, South America) were sampled at two stations from June 1989 until October 1990. A total of 52,989 individuals from 59 species, some still incompletely identified, were collected. Three families, Engraulidae, Gobiidae and Sciaenidae, accounted for over 97% of the total number of juveniles. The analysis of data over this period showed low diversity, and a difference in diversity between the two sampling locations (H′ = 1.24 and 1.68). The results conform to some theoretical models of abundance that suggest a relative equilibrium of juvenile assemblages. In contrast, the seasonal variations in diversity and abundance and the results of a correspondence analysis showed significant differences in species distribution and in their relative abundance at the two sampling locations at certain periods, mainly in the rainy season. Our study indicates that, in spite of an apparent stability, the year to year variation in salinity and freshwater inputs could affect juvenile recruitment of some species and induces modifications in the composition of larval and juvenile estuarine fish assemblages.     

Spatial and temporal variation of heavy metals in a tropical estuary

The lower part of the Coatzacoalcos River has great industrial development in which high pollution has been reported. Surface sediments of this area were studied over a year to observe spatial and seasonal sedimentological and chemical variations. Higher metal concentrations were found during the dry season, Pajaritos Dock and Teapa sampling points showing the highest values. Ni (182 ppm) and Co (37 ppm) concentrations are elevated relative to other estuarine areas. Metal normalization against Al₂O₃ content shows contaminant input in areas where urban and industrial discharges exist. A cluster analysis of the data separates sediment samples from the different sampling trips, suggesting the dynamic nature of the sediments. Through the statistical t-test, metal enrichment of Cd, Cu, Cr, Ni, Pb, and Zn was evaluated and compared with metal concentration in sediments of the river higher parts. The percentage of bioavailable metals is a function of the physicochemical characteristics of the system.     

Speciation of trace metals in sediments of a tropical estuary

Axial surveys were performed in the two river tributaries of the Cochin estuary, SW India during November 1988. Surficial sediments were subjected to sequential chemical extractions to delineate five metal fractions, namely, exchangeable, carbonate bound, easily reducible, organic/sulfide bound, and residual. The results indicated selective accumulation of Mn and Ni in carbonate bound and organic/sulfide forms, along with marginal amounts of Co in the exchangeable fraction. Large portions of Fe and Cr occurred in the residual fraction, whereas composite fractionation of Zn species was noticed. The exchangeable fractions of Fe and Cr as well as of easily reducible cobalt were below detection limits. The levels of Cr and Zn indicate anthropogenic inputs in this estuary, whereas Co and Ni show regional contamination exceeding natural levels. The analytical speciation procedure helps to deduce the sedimental diagenetic processes in the estuarine environment.     

Fractionation of phosphorus in the sediments of a tropical estuary

Fractionation of phosphorus in the sediments of the Cochin estuary situated along the southwest coast of India was studied by applying sequential chemical extraction. The different forms of phosphorus were estimated seasonally (premonsoon, monsoon, and postmonsoon) under eight different schemes. The major forms of phosphorus analyzed were exchangeable P, anion exchangeable P, carbonate-bound P, labile and resistant organic P, Fe and Al P, calcium-bound P, and hydrolyzable surplus P. Quantitatively, the above fractions in isolation or in combination vary in content due to chemoestuarine variability and seasonal fluctuations. Changes in speciation have been noted in association with salinity variations in the waterway, especially following enhanced river runoff during the monsoon. The chemical forms of the sediment-bound phosphorus in the northern parts of this estuary have been shown to be modified by nonpoint sources. Sediment P fractionation defines the role of chemical speciation of phosphates (as nutrients) and is indicative of the processes controlling the pathways of P into the coastal waters. The changes in the exchangeable P, together with marked regional variations in calcium-bound P, exemplify the complex estuarine variability of phosphorus. Enhanced amounts of exchangeable P mark its appearence in high saline waters, signifying the presence of biologically available nutrient phosphorus. The calcium-bound P and hydrolyzable surplus P show significant relation with sediment organic carbon and Fe whereas other forms do not exhibit any marked covariation. The Ca and Na NTA extraction scheme is very specific in its selectivity.     

Sedimentation in a tropical, microtidal, wave-dominated coastal-plain estuary

The Mono estuary is an infilled, microtidal estuary located on the wave-dominated Bight of Benin coast which is subject to very strong eastward longshore drift. The estuarine fill comprises a thick unit of lagoonal mud deposited in a ‘central basin’between upland fluvial deposits and estuary-mouth wave-tide deposits. This lagoonal fill is capped by organic-rich tidal flat mud. In addition to tidal flat mud, the superficial facies overlying the ‘central basin’fill include remnants of spits resting on transgressive/washover sand, an estuary-mouth association of beach, shoreface, flood-tidal delta and tidal inlet deposits, and a thin sheet of fluvial sediments deposited over tidal flat mud. After an initial phase of spit intrusion over the infilled central basin east of the present Mono channel, the whole estuary mouth became bounded by a regressive barrier formed from sand supplied by the Volta Delta during the middle Holocene eustatic highstand. Barrier progradation ceased late in the Holocene following the establishment of an equilibrium plan-form shoreline alignment that allowed through-drift of Volta sand to sediment sinks further downdrift. Over the same period, accretion, from fluvially supplied sediments, of the estuarine plain close to the limit of spring high tides, or, over much of the lower valley, into a fluvial plain no longer subject to tidal flooding, induced marked meandering of the Mono and its tidal distributaries in response to confinement of much of the tidal prism to these channels. The process resulted in erosion of spit/washover and regressive barrier sand, and in reworking of the tidal flat and floodbasin deposits. The strong longshore drift, equilibrium shoreline alignment and the year-round persistence of a tidal inlet maintained by discharge from the Mono and from Lake Ahémé have resulted in a stationary barrier that is reworked by a mobile inlet. The Mono example shows that advanced estuarine infill may result in considerable facies reworking, obliteration of certain facies and marked spatial imbrication of fluvial, estuarine and wave-tide-deposited facies, and confirms patterns of sedimentary change described for microtidal estuaries on wave-influenced coasts. In addition, this study shows that local environmental factors such as sediment supply relative to limited accommodation space, and strong longshore drift, which may preclude accumulation of sediments in the vicinity of the estuary mouth, may lead to infilled equilibrium or near-equilibrium estuaries that will not necessarily evolve into deltas.     

Strontium and its isotopes in Canadian rivers: Fluxes and global implications

Systematic sampling of the 39 largest Canadian rivers shows that the weighted average ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio in the dissolved load is 0.7111, similar to previous measurements on such large rivers as the Amazon and Mississippi. Consequently, we believe that the above estimate is likely representative of the global average. This imposes a limit of 6.5 × 10¹¹g yr^?1 on the amount of Sr exchanged with basalts in hydrothermal cells on mid-oceanic ridges. Evaluation of geological information suggests that Sr from silicate sources is of considerable importance for all but the largest Canadian rivers. The latter have chemical and isotopic composition consistent with ~4:1 carbonate vs. silicate derivation of Sr, but such interpretation is not unique. In terms of their water discharge, the 39 Canadian rivers studied account for 4.2% of the world total and their weighted average concentrations for other dissolved solutes are: TDS 176 ppm, Ca 18 ppm, Cl 6.8 ppm and Sr 84 ppb.     

Distribution of dissolved carbohydrates and uronic acids in a tropical estuary,India

Carbohydrates including uronic acids are among the active components of dissolved organic carbon, and play an important role in biogeochemical cycling of organic carbon in marine environments. In order to understand their distribution, concentrations of total dissolved carbohydrate (TCHO), dissolved polysaccharide (PCHO), dissolved monosaccharide (MCHO), and dissolved uronic acid (URA) were measured in the Mandovi estuary, west coast of India during the monsoon and premonsoon seasons. The estuary experienced nearly fresh water condition during the monsoon season and marine condition during the pre-monsoon season. Concentrations of TCHO, MCHO and URA ranged from 17.7 to 67.3 μM C, 4.1 to 15.5 μM C and 2.3 to 10.8 μM C, and their contribution to dissolved organic carbon (DOC) varied from ∼11 to 60%, 2.5 to 9.7%, and 1.8 to 5.3%, respectively. PCHO accounted for ∼52 to 92% of the TCHO. Generally, concentrations and yields of TCHO species were greater during the monsoon season. Phytoplankton abundance and bacterial cell numbers influenced the distribution of TCHO in the pre-monsoon season but not during the monsoon season. Transport of TCHO rich (11 to 60%) dissolved organic matter from the Mandovi estuary to the coastal waters during the monsoon season may affect ecosystem function by fueling biological activity of heterotrophic micro-organisms.     

Strontium isotopes in magnesites from Permian and Triassic strata,Eastern Alps

The Sr isotopic composition of sediment-hosted magnesites in Permian and Scythian series of Upper Austroalpine units (Eastern Alps) has been determined. The results suggest diagenetic-metasomatic magnesite formation by Mg-rich pore solutions. The depositional environment of the magnesite-bearing rocks is reflected by different isotopic compositions with initial ⁸⁷Sr/⁸⁶Sr ratios close to contemporaneous sea water in marine sediments (0.7071–0.7083) and higher ratios being typical for lacustrine and coastal environments influenced from the hinterland (0.7133–0.7139). Coarser grained recrystallized magnesite and magnesite veins show a distinct increase in their Sr isotopic ratios (0.7202–0.7220) which can be attributed to metamorphic fluids of Eoalpine age. The findings of these magnesite occurrences, which have been affected only by very low-grade metamorphism, are compared with similar results from spar magnesites associated with metamorphosed Paleozoic sedimentary rocks. A similar genetic model is proposed for the first magnesite mineralization in those Paleozoic strata, but with variably intense later recrystallisation during metamorphism.     

Spatial sediment variability in a tropical tide dominated estuary: Sources and drivers

Surficial sediment composition and spatial variability reflect the dynamics and level of natural and anthropogenic impact in estuarine systems. The aim of this study is to evaluate some key environmental and sedimentary variables, as well as to evaluate the current environmental quality in the tide-dominated Caravelas estuarine system (Brazil). Sixty-five surficial sediment samples were studied for grain size as well as calcium carbonate, total organic carbon, total nitrogen, metals, semi-metals and rare earth elements and for organic matter δ¹³C. Based on the spatial distribution of these data and summarizing our findings, three sectors can be individualized in the Caravelas estuarine system: i. Barra Velha inlet; ii. the main channel of the Caravelas estuary, and iii. the channel interconnecting Caravelas and Nova Viçosa estuaries. In the inlet the sedimentary organic matter is provided essentially by marine sources, which corroborates the small continental input. Freshwater dissolved organic carbon and particulate organic carbon occur in the interconnecting channel, proving the occurrence of the residual transport towards the Caravelas estuary, with continental contribution towards Caravelas River. The geochemical fingerprint indicates that the Barreiras Group, composed by Neogene terrigenous deposits, located west of the study area, as an important source of terrigenous material to the entire Caravelas estuary system. The higher values of heavy rare earth elements (between 20 and 30 mg kg⁻¹) in the northern sector of the study area may be related to the high degree of chemical weathering in magmatic or metamorphic rocks, which occur to the north of the study area.     

Mobilization of trace metals in a tropical turbid estuary influenced by a monsoon season

The selective removal of trace metals by suspended matter in high turbidity zones plays a major role in the fluvial transport of terrigenous metals to the marine environment. The seasonal longitudinal variability of trace elements (Cu, Zn, Cd, Ni, Pb, Fe, and Mn) in Cochin estuary, a tropical positive estuary, was studied and the results were compared with the prevailing situation in other subtropical waterways. The hydrodynamical features showed increasing turbidity downstream with increasing salinities during both the seasons. In contrast with the temperate estuaries where the development of turbidity maxima causes the removal of metals, the estuaries of tropics modify the fluvial transport of metals by the way of redistribution between the dissolved and particulate fractions in the intermediate salinities. In Cochin estuary, the distributional features of trace metals are primarily influenced by the variations in salinities and river discharges. Consequently, this gives rise to two different types of distributional patterns: (1) during premonsoon, the estuarine reactivity is more pronounced and hence, mid-estuarine solubilization of the particulate metal appears to play a prominent role in controlling the fluxes of trace metals studied and (2) but during monsoon, the hydrological conditions influence the downstream transport of the metals more by physical dilution than chemical reactivity.     

Strontium isotopes as tracers of airborne fly ash from coal-fired power plants

Fly ash generated by coal-fired power plants is in part collected by filters in the emission stacks while a small portion is vented into the atmosphere. Since many of the coalfired power plants in the western United States are located in the desnrt, the ability to monitor fly ash emissions requires a chemical tracer that utilizes desert soil and plant interactions with the fly ash deposited in the desert environment. This investigation presents the results of a controlled greenhouse experiment in which a native desert plant, the brittlebush (Encelia farinosa), was grown on admixtures of desert soils and fly ash. The fly ash is strongly enriched in Sr and the brittlebush is a Sr accumulator. The data demonstrate that (1) the brittlebush isotopically equilibrates with desert soils whose fly ash components are as low as 0.25% by weight, (2) the fly ash Sr is apparently more available to the plant, than Sr derived from the soils, and (3) the difference between the⁸⁷Sr/⁸⁶Sr ratio of the fly ash (0.70807) and soils (0.71097 to 0.71117) warrants further investigations in the natural environment to determine the practicality of this method as a natural tracer of fly ash in the environment.     

Biogeochemical facsimile of the organic matter quality and trophic status of a micro-tidal tropical estuary

Seasonal studies were carried out from 21 stations, comprising of three zones, of Cochin Estuary, to assess the organic matter quality and trophic status. The hydographical parameters showed significant seasonal variations and nutrients and chlorophylls were generally higher during the monsoon season. However, chemical contamination along with the seasonal limitations of light and nitrogen imposed restrictions on the primary production and as a result, mesotrophic conditions generally prevailed in the water column. The nutrient stoichometries and δ ¹³C values of surficial sediments indicated significant allochthonous contribution of organic matter. Irrespective of the higher content of total organic matter, the labile organic matter was very low. Dominance of carbohydrates over lipids and proteins indicated the lower nutritive aspect of the organic matter, and their aged and refractory nature. This, along with higher amount of phytodetritus and the low algal contribution to the biopolymeric carbon corroborated the dominance of allochthonous organic matter and the heterotrophic nature. The spatial and seasonal variations of labile organic components could effectively substantiate the observed shift in the productivity pattern. An alternative ratio, lipids to tannins and lignins, was proposed to ascertain the relative contribution of allochthonous organic matter in the estuary. This study confirmed the efficiency of an integrated biogeochemical approach to establish zones with distinct benthic trophic status associated with different degrees of natural and anthropogenic input. Nevertheless, our results also suggest that the biochemical composition alone could lead to erroneous conclusions in the case of regions that receive enormous amounts of anthropogenic inputs.     

Physico-chemical seasonal variability of a tropical estuary: major and minor elements in water and air

The lower reaches of the Coatzacoalcos River in southeast Mexico is an area of intense industrial development. The physico-chemical characteristics of the area have exhibited differences over the years. Apparently from the associated outcroppings of limestone in the Uxpanapa River Basin, the major elements that are dissolved show higher concentrations of Ca, Mg and HCO₃^– in the waters supplied by this river. The water in the Calzadas River contains high concentrations of Ca, SO₄ and HCO₃^– that are associated with the saline domes crossed by this river. Due to industrial discharges, the sulfate concentration is very high in the water and air during April. Nitrate concentration diminishes with salinity. Higher nitrate as well as nitrite and ammonia levels are present during flood season. Phosphate concentration, associated with high oxygen levels, is higher in January. Zn, Cu and Cr are higher during the dry season (April) when dilution is minimal and low levels of TOC are present. The smaller concentrations of Zn and Cu observed in January are associated with high TOC values in water. The lower levels of Cr present in August are associated with high amounts of suspended matter. Pajaritos Lagoon and Teapa-L, with large industrial discharges, have the highest nutrient and dissolved metal concentrations in the area. Air particles smaller than 2.5 m contain Fe, V, Ti, Cu, Zn, and high amounts of S. These anomalous concentrations of sulfates and metals are attributed to anthropogenic sources.     

Depositional environment of mudflats and mangroves and bioavailability of selected metals within mudflats in a tropical estuary

Four sediment cores representing adjacent mudflat and mangrove sub-environments of middle estuary (Shastri) were analyzed for sand, silt, clay, and organic carbon. Total metal concentration of iron (Fe), manganese (Mn), nickel (Ni), zinc (Zn), chromium (Cr), copper (Cu), cobalt (Co), and lead (Pb) and chemical speciation of Fe, Mn, and Co on selected samples was also carried out on mudflat cores. The sediments in the upper middle estuary were found to be deposited under highly varying hydrodynamic energy conditions; whereas lower middle estuary experienced relatively stable hydrodynamic energy conditions with time. The tributary joining the river near the upper middle estuary is found to be responsible for the addition of enhanced organic carbon and metal concentrations. Speciation study indicated Fe and Co are from natural lithogenic origin while Mn is derived from anthropogenic sources. Higher Mn and Co than apparent effects threshold can pose a high risk of toxicity to organisms associated with these sediments.     

Sediment transport and trapping in the Hudson River estuary

The Hudson River estuary has a pronounced turbidity maximum zone, in which rapid, short-term deposition of sediment occurs during and following the spring freshet. Water-column measurements of currents and suspended sediment were performed during the spring of 1999 to determine the rate and mechanisms of sediment transport and trapping in the estuary. The net convergence of sediment in the lower estuary was approximately 300,000 tons, consistent with an estimate based on sediment cores. The major input of sediment from the watershed occurred during the spring freshet, as expected. Unexpected, however, was that an even larger quantity of sediment was transported landward into the estuary during the 3-mo observation period. The landward movement was largely accomplished by tidal pumping (i.e., the correlation between concentration and velocity at tidal frequencies) during spring tides, when the concentrations were 5 to 10 times higher than during neap tides. The landward flux is not consistent with the long-term sediment budget, which requires a seaward flux at the mouth to account for the excess input from the watershed relative to net accumulation. The anomalous, landward transport in 1999 occurred in part because the freshet was relatively weak, and the freshet occurred during neapetides when sediment resuspension was minimal. An extreme freshet occurred during 1998, which may have provided a repository of sediment just seaward of the mouth that re-entered the estuary in 1999. The amplitude of the spring freshet and its timing with respect to the spring-neap cycle cause large interannual variations in estuarine sediment flux. These variations can result in the remobilization of previously deposited sediment, the mass of which may exceed the annual inputs from the watershed.     

Pore water trace metal chemistry in polluted sediments of a tropical estuary of SE Brazil

The Sepetiba Bay is a shallow water body semi enclosed located on the west side of Rio de Janeiro City. Almost 80% of flesh water discharge, from the St Francisco canal, coming from the northern side of the bay develops an estuarine environment. Fishing and tourism are some of the most important economic activities in the area. During 35 years a zinc/cadmium smelter has polluted the bay. The objective of this investigation is to demonstrate the diagenetic processes and cadmium remobilization into pore water from the contaminated sediments. Two sites were selected to compare diagenetic processes. Site P1 is located next to domestic effluents discharge into the bay and approximately 20km away from the smelter. Site P2 is located near the same smelter and next to the Mazomba estuary, which is not influenced directly by domestic effluents. Peeper samplers of 25 cells with a resolution of 2.5 cm were deployed at both the sites. After a 3-weeks period of equilibrium, the pore waters were separated from the cells and analyzed immediately （within 24 h） for alkalinity, NH3 and reactive soluble phosphorus on a spectrophotometer. An ICP-AESΣH2S spectrometer was used to analyze Na, Mg, Li, Ba, Sr, Si, Fe and Mn. Total and labile dissolved Cd in pore waters were determined by differential-pulse stripping voltametry. The dissolved constituents in the pore waters have shown that the intensities of diagenetic reactions are different between sites. The reactions are stronger at site P1 site than at site P2, especially between 7.5 cm and 22.5 cm, which is evident by the organic rich sediment.     

Geochemistry of Fe and Mn in surficial sediments of a tropical river and estuary,India—a granulometric approach

Geochemical characteristics of Fe and Mn in sand, silt, and clay fractions as well as in bulk sediments of the tropical perennial Muvattupuzha river and the Central Vembanad estuary of the southwest coast of India have been studied and discussed. The results of a physical fractionation study of Fe and Mn indicated a substantial increase in the content of these metals in silt and clay fractions above that in sand. The riverine silt and clay fractions account for two to three times the enrichment of Fe and Mn than the corresponding sand fraction; the estuarine counterparts indicate four to eight times the enrichment. The observed enrichment of Fe and Mn towards the more finer size grades is mainly due to the increased surface area of the finer clastics, which in turn increase the absorptive ability. However, the mineralogical diversities of the three size fractions also influence the enrichment of Fe and Mn. The spatial distribution of Fe and Mn indicates a marked decrease in the content of the latter than the former towards the high saline zones of the river and the estuary. This variation could be due to the higher solubility of Mn towards the high saline zones of the aquatic environment where reducing condition prevails most of the year.     

Solute transport through a deforming porous medium

Solute transport through a porous medium is typically modelled assuming the porous medium is rigid. However, many applications exist where the porous medium is deforming, including, municipal landfill liners, mine tailings dams, and land subsidence. In this paper, mass balance laws are used to derive the flow and transport equations for a deforming porous medium. The equations are derived in both spatial and material co‐ordinate systems. Solute transport through an engineered landfill liner is used as an illustrative example to show the differences between the theory for a rigid porous medium, and small and large deformation analysis of a deforming porous medium. It is found that the large deformation model produces shorter solute breakthrough times, followed by the small deformation model, and then the rigid porous medium model. It is also found that it is important to include spatial and temporal void ratio variations in the large deformation analysis. It is shown that a non‐linear large deformation model may greatly reduce the solute breakthrough time, compared to a standard transport analysis typically employed by environmental engineers. Copyright © 2002 John Wiley & Sons, Ltd.     

Anthropogenic impacts recorded in the sediments of Lunawa, a small tropical estuary, Sri Lanka

The Lunawa Estuary has been selected as a model for studying the long-term diagnoss of tropical estuarine pollution and its impact on ecosystems. Surface and short-core sediments from the Lunawa Estuary were collected, and analyzed for total organic carbon (TOC), nitrogen, sulfur and hydrocarbon contents, hydrogen index and other related sediment properties. Water quality and surface sediment data indicate that the Lunawa Estuary is presently an anoxic water body. The upper part of the sediment cores, characterized by very high TOC values of more than 10%, and absence of bioturbation along with strong laminations indicate anoxic water since 1970 AD, determined by ¹⁴ C dating. However, before 1970 AD, lower TOC content and presence of bioturbation and homogenous sediments with animal traces suggest the presence of oxic bottom water and thus a much better physicochemical condition. The lower part of the cores may also suggest the influence of gradual global warming. Regular laminations in the upper portions of the cores probably resulted from monsoon pulses with material preserved under anoxic condition.