Major and trace element associations in limestones and dolomites

Selective chemical separations of mineralogical constituents of limestones (Carboniferous limestones from the Isle of Man, and Lincolnshire limestone, Middle Jurassic, Lincolnshire) and dolomites (from Carboniferous limestone, Isle of Man) using dilute acetic acid and hydrogen peroxide have been used and the fractions obtained analysed to evaluate mineralogical associations of trace and major elements. Ca, Mg, Mn and Sr are mainly restricted to the carbonate fraction. Fe is found in carbonates, particularly dolomite, and also in sulphides with Zn, Cu, Ni and Pb, and with V and Cr and other traces in “residual” silicate minerals.It is concluded that mineralogical associations of trace elements are complex, and cannot be easily determined by statistical analysis. Selective chemical-separation methods of analysis offer direct indication of element associations with no loss of data. Calculated average concentrations in various fractions of analysed rocks (58 limestones and 19 dolomites) are tabulated.     

Major and trace element geochemistry of superficial sediments and suspended particulate matter of shallow saline lakes in Eastern Austria

General geochemical parameters of water, superficial sediments, and suspended particulate matter (SPM) were determined from small shallow saline lakes (soda ponds) as well as from lake Neusiedlersee in eastern Austria. Additionally, instrumental neutron activation analysis (INAA) was used to determine the distribution of major, rare earth and other trace elements in superficial sediments and SPM. Chemical results show remarkable differences in salinity and ionic strength between the investigated ponds. Anthropogenic effects, such as drawdown of ground water level and a loss of lake water due to drainage, are clearly reflected in obtained chemical and geological data. Due to a strong dependence of the complexation and scavenging behavior of the rare earth elements (REE) on ionic strength, a significant difference between REE concentrations in soda ponds with different anthropogenic impact was found. The content and composition of authigenic evaporitic minerals in superficial sediments and SPM clearly differ with a fluctuating water level and salt concentration. Furthermore, we determined the distribution of major and trace elements in superficial sediments of a nearby fluvial system. Our results show a clear correlation between REE superficial sediment concentrations in anthropogenically degraded soda ponds and fluvial system. Therefore, we assume that REE concentrations of sediments and SPM are suitable for the study of geochemical changes of inland saline lakes due to anthropogenic impacts on water balance.     

Historical trace element distribution in sediments from the Mississippi River delta

Five sediment cores were collected on the shelf of the inner Mississippi Bight in June 2003 for a suite of radionuclides to establish geochronologies and trace elements to examine patterns of contaminant deposition and accumulation. Core sites were chosen to reflect a matrix of variable water depths, proximity to the Mississippi River mouth as the primary source for terrigenous particles, and extent and duration of summertime water column hypoxia. The vertical distribution of^239,240Pu and²¹⁰Pb_xs(=²¹⁰Pb_total−²²⁶Ra) provided reliable geochronological age constraints to develop models for mass accumulation rates and historic trace element inputs and variations. Mass accumulation rates ranged from 0.27 to 0.87 g cm⁻²yr⁻¹ and were internally consistent using either²¹⁰Pb_xs or^239,240Pu. Measured inventories of¹³⁷Cs,^239,240Pu, and²¹⁰Pb_xs were compared to atmospheric deposition rates to quantify potential sediment focusing or winnowing. Observed variability in calculated mass accumulation rates may be attributed foremost to site-specific proximity to the river mouth (i.e., sediment source), variability in water depth, and enhanced sediment focusing at the Mississippi River canyon site. Trace element concentrations were first normalized to Al, and then Al-normalized enrichment factors (ANEF) were calculated based on preanthropogenic and crustal trace element abundances. These ANEFs were typically >1 for V and Ba, while for most other elements studied, either no enrichment or depletion was observed. The enrichment of Ba may be related, in part, to the seasonal occurrence of oxygen-depleted subsurface waters off the Mississippi River delta, as well as being an ubiquitous byproduct of the petroleum industry.     

Elevated stream trace and minor element concentrations in the foreland of receding tropical glaciers

Globally, the ongoing retreat of mountain glaciers will ultimately diminish fresh water supplies. This has already begun in watersheds with greatly reduced glacial coverage. Still unknown are the affects of glacial retreat on downstream water quality, including the threats to human and ecosystem health. In the Cordillera Blanca, retreating glaciers have exposed sulfide-rich rock outcrops, negatively affecting the quality of the glacial meltwater. This study has evaluated glacial melt stream hydrogeochemistry in the sulfide-bearing Rio Quilcay watershed (∼9°27′S, ∼77°22′W) during the 2008 dry season. Surface water samples were collected from the upper 12 km of the watershed during the 2008 dry season. Dissolved (0.4 μm) and unfiltered acidified (pH < 2) Al, Co, Cu, Fe, Ni, Mn, Pb, Zn and dissolved major ions and organic C (DOC) concentrations were quantified and pH and temperature were measured in the field. Twenty of 22 stream samples had pH values below 4, generating significantly (p < 0.01, α = 0.05) greater cation denudation normalized to discharge than other worldwide glacier-fed streams. Additionally, dissolved trace and minor element concentrations were comparable to acid mine drainage. Non-conservative dissolved element behaviors resulted from adsorption/desorption reactions in tributary mixing zones. At low pH values, hydrous Fe oxides acted as the dominant sorption surfaces. The poor water quality observed in Cordillera Blanca headwaters coupled with the likely exposure of additional sulfide-rich outcrops from ongoing glacial retreat may pose water quality challenges.     

Geochemistry of trace element in carbonaceous sediments from recent seas and oceans

Published and original data on the contents of 50 elements in carbonaceous sediments from seas (Black, Baltic, and Caspian) and fertile oceanic shelves (shelves of Namibia, Peru, Chile, and California) are generalized. The comparison of these results with the average composition of ancient carbonaceous shales reveals both similarities and differences in the distribution of indicator trace elements (Re, Hg, Se, Ag, Cd, Tl, U, Mo, As, Ni, and Zn). Correlation coefficients were analyzed to determine the characteristic element associations. It is established that oceanic carbonaceous sediments are closer in composition to carbonaceous shales than their marine analogues, which is related to the differences in sedimentation conditions, including hydrological, hydrochemical, and biogeochemical factors. The role of anoxic environment in the accumulation of chalcophile elements in sediments is estimated. The comparison of the contents of some mobile trace elements in oceanic water and carbonaceous sediments of modern oceans demonstrates that the water composition affects the composition of carbonaceous sediments and can be used for deciphering the composition of ancient ocean water.     

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。     

Transportation and evolution of trace element bearing phases in stream sediments in a mining – Influenced basin (Upper Isle River,France)

Arsenic-bearing stream sediments enter the Upper Isle River, an Au mining-influenced basin (France), by the discharge of mining sites, tailings runoff and weathering of mineralized veins in granites and gneiss. Some fresh ochreous As-rich deposits on the river banks and in floodplains are identified as additional As-rich point sources (As between 0.07 and 6.5 wt.%). The <63 μm fraction of stream sediments contains elevated As bulk concentrations, ranging from 160 to 890 mg/kg, compared to the geochemical background (70 mg/kg on average). It is also enriched in Cd, Hg and W. Spatial variations of these trace elements show 3 significant increases corresponding to the 3 drained mining districts. They decrease down river but are still enriched 30 km downstream of the mining districts due to downstream transportation. Three types of trace element-bearing phases have been identified as: (i) detrital primary sulfides, with high in situ As percentages (up to 43.7 wt.%). They also carry significant amounts of W according to the differences in chemical compositions of the total and light <63 μm fractions. These sulfide particles do not show any sign of alteration in the oxygenated stream sediments; (ii) Secondary Fe–Mn oxyhydroxides,some with very high in situ As₂O₅ concentrations (up to 59.8 wt.%) and with about 40% of the total Cd composition. They occur as fresh precipitates in the river banks and floodplains and as discrete particles in stream sediments and (iii) Al–Si fine-grained phases. Their major element composition is highly variable with in situ As₂O₅ concentrations ranging between 430 and 5020 mg/kg. This type of solid phase is also the major carrier of Hg.     

Major and trace element variation in ilmenite in the Skaergaard Intrusion: petrologic implications

Ilmenite separates from the floor (LS), roof (UBS), and wall (MBS) sequences of the Skaergaard Intrusion were analyzed for major and trace elements using DCP-AES and ICP-MS techniques. In all three sequences, FeO progressively increases, and MgO and Al₂O₃ progressively decrease with differentiation. Although trace element abundances are, in general, higher in UBS ilmenite than in MBS and LS ilmenite, all three sequences have similar trends for trace element abundance vs. crystallization. Ba, Cs, Rb, Sr, Th, U, Y, and the REEs are excluded elements in ilmenite, and remained at low abundances during differentiation. Cr, Ni, Sc, and V are included elements in ilmenite and other mafic phases, and decreased during differentiation. V contents in ilmenite, however, do not decrease significantly until the upper part of the middle zone, suggesting that magnetite did not begin to affect the magma differentiation trend until much later than when it first appears in the intrusion. Hf, Nb, Ta, and Zr, which are strongly excluded elements in silicates, are included elements in ilmenite. The element ratios Zr/Hf, Y/Ho, Nb/Ta, and U/Th are relatively constant in Skaergaard ilmenite from different parts of the intrusion, suggesting that fluid transport did not significantly effect these elements during differentiation or post-solidification cooling. Calculated partition coefficients for ilmenite in the Skaergaard Intrusion are similar to those reported from previous studies of lunar and terrestrial basalts and kimberlites, and for most elements are significantly lower than those reported for ilmenite in rhyolitic magma. Similar D_i's for Zr, Hf, Nb, and Ta suggest that ilmenite crystallization did not significantly affect Zr/Nb or Hf/Ta in the Skaergaard magma, but the ratios of Zr, Hf, Nb, or Ta to other high field strength elements, such as Th, U, Y, or the REEs, may have been altered by ilmenite fractionation.     

Major and trace element geochemistry in upper Ganga river in the Himalayas, India

Chemical weathering and resulting water compositions in the upper Ganga river in the Himalayas were studied. For the first time, temporal and spatial sampling for a 1 year period (monthly intervals) was carried out and analyzed for dissolved major elements, trace elements, Rare Earth Elements (REE), and strontium isotopic compositions. Amounts of physical and chemical loads show large seasonal variations and the overall physical load dominates over chemical load by a factor of more than three. The dominant physical weathering is also reflected in high quartz and illite/mica contents in suspended sediments. Large seasonal variations also occur in major elemental concentrations. The water type is categorized as HCO₃^––SO₄^2––Ca²⁺ dominant, which constitute >60% of the total water composition. On an average, only about 5–12% of HCO₃^– is derived from silicate lithology, indicating the predominance of carbonate lithology in water chemistry in the head waters of the Ganga river. More than 80% Na⁺ and K⁺ are derived from silicate lithology. The silicate lithology is responsible for the release of low Sr with extremely radiogenic Sr (⁸⁷Sr/⁸⁶ Sr>0.75) in Bhagirathi at Devprayag. However, there is evidence for other end-member lithologies for Sr other than carbonate and silicate lithology. Trace elements concentrations do not indicate any pollution, although presence of arsenic could be a cause for concern. High uranium mobilization from silicate rocks is also observed. The REE is much less compared to other major world rivers such as the Amazon, perhaps because in the present study, only samples filtered through <0.2 m were analysed. Negative Eu anomalies in suspended sediments is due to the excess carbonate rock weathering in the source area.     

Assessment of trace metals contamination in stream sediments and soils in Abuja leather mining,southwestern Nigeria

This study is aimed at determining the level of environmental degradation as well as the concentration of trace elements in soil and stream sediments in order to evaluate the environmental impact of the mining operation. Twenty-five (25) soils and ten (10) stream sediment samples were collected from the study area. The physicochemical parameters were determined using appropriate instrumentation with the aid of a digital pH meter (Milwaukee meter) to measure the pH and electrical conductivity, total dissolved solids, moisture content and loss on ignition of the soil and stream sediment samples. The pH of the soil sample ranged from (6.10 to 7.19); Electrical conductivity ranged from (21.3 to 279.4 µS/cm), moisture content varied from (0.60% to 7.20%), and the LOI ranged from (2.03% to 18.62%). The results of the analysis showed that the concentrations of the trace elements in the soils and stream sediment samples were slightly higher than the background values. Plots of the trace elements in stream sediment samples show moderate, consistent decrease downstream except at points where there was mine water discharge into the main river. The pollution levels of heavy metals were examined in stream sediment and soil samples using different assessable indices, such as the enrichment factor, which showed significant-moderate enrichment for Cr, Th, Nb, Zn, Pb, Y and Zr and the geo-accumulation index, which showed practically moderate contamination with Cr, Ni and Sr based on regional background reference values. Geo-accumulation index and contamination index for soils and stream sediment revealed uncontaminated to moderate contamination. Likewise, elements with moderate contamination were Cr, Ni and Sr. The Pearson correlation showed that there were significant positive associations among selected metals in soil and stream sediment samples.     

四川大岩子Pt-Cu矿床水系沉积物中的地球化学异常特征及外围找矿预测

大岩子-清水河地区的 1∶5万 Pt- Pd水系沉积物测量表明,大岩子 Pt- Cu矿床的指示元素有 Pd、Pt、Au、Cu、Ni、As、Ag、Cd、F、Hg、Pb、Zn、S和 Se,地球化学异常具有水平分带的特征,即从矿床向外的异常元素依次为 Pd、Pt、Au- Cu、Ni- As、Ag- Cd、F、Hg- Pb和 Zn.试验研究表明, 1∶5万水系沉积物测量是找寻 Pt、Pd矿床的有效方法.推测西王庙周围有 Pt、Pd矿的找矿远景.     

Particulate trace metal speciation in stream sediments and relationships with grain size: Implications for geochemical exploration

Sediment samples were collected from streambeds in an undisturbed watershed in eastern Quebec (Gaspé Peninsula). Two sampling sites were located on a stream draining an area of known mineralization (Cu, Pb, Zn) and two on a control stream. The sediment samples were separated into 8 distinct size classes in the 850 μm to <1 μm size range by wet sieving, gravity sedimentation or centrifugation. Each sediment subsample was then subjected to a sequential extraction procedure designed to partition the particulate heavy metals into five fractions: (1) exchangeable; (2) specifically adsorbed or bound to carbonates; (3) bound to Fe-Mn oxides; (4) bound to organic matter; (5) residual. The following metals were analyzed in each extract: Cu, Pb, Zn; Fe, Mn.Comparison of samples from the mineralized area with control samples revealed the expected increase in total concentrations for Cu, Pb and Zn. Non-detrital metals were mainly associated with Fe oxides (specifically adsorbed; occluded) and with organic matter or resistant sulfides. For a given sample, variation of trace metal levels in fractions 2 and 3 with grain size reflected changes in the available quantities of the inorganic scavenging phase (FeOx/MnOx); normalization with respect to Fe and Mn content in fraction 3 greatly reduced the apparent dependency on grain size.The results of this study suggest that a single reducing extraction (NH₂OH.HCl) could be used advantageously to detect anomalies in routine geochemical surveys. A second leaching step with acidified H₂O₂ could also be included, as the trace metal concentrations in fraction 4, normalized with respect to organic carbon content, also showed high {anomaly/background} ratios.     

Isotope and trace element geochemistry of sediments from the Barbados Ridge-Demerara Plain region,Atlantic Ocean

Twenty-four piston core sediment samples and 13 sediments and 3 basalts from DSDP Leg 78 Site 543 were analyzed for Sr, Nd and Pb isotopic compositions. The results show sediment with highly radiogenic Pb${}^{206}\text{Pb}{}^{204}\text{Pb}$ up to 19.8) and rather radiogenic Sr and unradiogenic Nd has been deposited in the region since the Cretaceous. The source of this sediment is probably the Archean Guiana Highland, which is drained by the Orinoco River. Pb and Sr isotopic compositions and sediment thickness decrease and${}^{143}\text{Nd}{}^{144}\text{Nd}$ increases northward due to a decrease in turbiditic component. This decrease is partly due to the damming action of basement ridges. Rare earth concentrations in the sediments are somewhat low, due to the abundance of detrital and biogenic components in the sediment and rapid sedimentation rates. Both positive and negative Ce anomalies occur in the surface sediments, but only positive Ce anomalies occur in the Site 543 sediments. It is unlikely that sediment subducted to the source region of Lesser Antilles arc magmas could be the cause of negative Ce anomalies in those magmas.Isotopic compositions of Site 543 basalts show some effect of contamination by seawater-basalt reaction products and sediments. Beyond this, however, they are typical of “normal” depleted MORB.     

Geochemical features of rocks,stream sediments,and soils of the Fiume Grande Valley (Calabria,Italy)

The role of both natural weathering and anthropogenic pollution in controlling the distribution of major oxides and several trace elements in soils, stream sediments, and rocks of the Fiume Grande catchment was evaluated. The contents of major oxides and trace elements in soils appear to be governed by weathering and pedogenetic processes, although the use of fertilizers in agriculture could also partly affect K₂O and P₂O₅ contents. Stream sediments have concentrations of major oxides (except CaO) very similar to soils, as relevant amounts of soil materials are supplied to the stream channels by erosive phenomena. In contrast, stream sediments have concentrations of Cr, Co, Ni, Zn, As, and Pb significantly higher than those of soils, probably due to different conditions and rates of mobility of these elements within the three considered matrices and/or disposal of wastes in the drainage network. Comparison of the concentrations of PHEs in soils with the maximum admissible contents established by the Italian law shows that these limits are too restrictive in some cases and too permissive in other ones. The approach of setting these limits with no consideration for the local geological–geochemical framework may lead to improper management of the territory and its resources. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Assessment of trace element geochemistry of Hampton Roads harbor and lower Chesapeake Bay area sediments

Acid extractable Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb. and Zn were determined in sediments from the Inner Virginia Shelf, and from shipping channels in the lower Chesapeake Bay and Hampton Roads, Virginia, harbor system. Data were evaluated by a variety of techniques Levels of Cd, Cu, Pb, and Zn exceeded average crustal abundances for most of the study sites. Cumulative frequency curves suggested that there were two major populations for all metals and perhaps a third and smaller, one for Cd, Cr, and Mn Plots of metal vs Fe indicated no anthropogenic inputs of metals for shelf and Chesapeake Bay channel sites, but suggested anthropogenic influences for all metals in several of the inshore sites. Enrichment factor calculations showed enrichment of Cd, Pb, and Zn with respect to average crustal abundances for all sites and of Cu for the industrial harbor system. A recommendation of this study for evaluation of environmental geochemical metals data is to utilize mean concentrations, cumulative frequency plots, and metal vs Fe and/or enrichment factor calculations when evaluating the pollution status of sediments.     

Major, trace and REE geochemistry of the Ganga River sediments: Influence of provenance and sedimentary processes

The sediments of the Ganga River from different depositional regimes in the Plain region such as the river channel, active flood-plain and the older flood-plain sediments from the inter-fluve region were analysed for major, trace and the rare earth elements (REEs). These are compared with catchment zone sediments of the river and probable source rocks in the Himalaya. The lower CIA values between 48 and 54.7 for the catchment sediments indicates that the sediments supplied to the Ganga Plain are chemically immature and subjected mostly to physical weathering due to higher erosion rates in the Himalaya. The CIA values ranging between 55 and 74, with average value of 59, 61.4 and 67 for sediments from the Plain's bed-load, active flood-plain and older flood-plain from the inter-fluve region indicates that silicate weathering of Ganga River sediments has occurred only after entering into the plains. This is likely because of higher residence time and change in the climate from cold-frigid in the Himalaya to tropical sub-humid in the plains. Therefore, the use of geochemical data on ancient system to infer climate in their source region may not always be true. Although the CIA values indicate a moderate chemical weathering in the plains, it is far from impressive. Dominance of physical weathering in the catchment region and lower degree of chemical weathering in the Plains indicate that weathering of sediments supplied by Himalayan Rivers, particularly the Ganga River may not have affected the atmospheric CO₂ to a significant level as is generally believed. Thus the net effect of the Himalaya on the CO₂ sequestration and consequent global cooling needs a re-evaluation.The plots of sediments in ternary diagram among La, Th, Sc and ratios involving Co/Th, La/Sc and Sc/Th indicate granitic to granodioritic source rocks to the sediments. The ratio plots involving relatively immobile Al₂O₃, TiO₂ and FeO along with REE plots suggest that out of the major Himalayan lithologies, gneisses and Cambro-Ordovician granites of HHCS have acted as the dominant source to the sediments.The plots of LogNa₂O/K₂O vs. LogSiO₂/Al₂O₃ and FeO/SiO₂ vs. Al₂O₃/SiO₂ diagrams show that the combination of processes including erosion, weathering, sorting and aeolian activity has together played a major role in progressively changing the chemistry from source rock to catchments bed-load to Plains bed-load, active flood-plains and the older inter-fluve sediments in the Ganga River system. The above plots demonstrate that as a result of above processes the ratios between the elements generally thought to be immobile and used in provenance studies does not always remain invariant and the linear trend line in the scatter gram between the two immobile elements show rotation around the fine grained end member.     

Rare-earth element geochemistry as a tracer for clarifying the provenance of the stream sediments in Namhan River, Korea

In the last forty years, the rare-earth elements （REEs） have been used as a powerful tool for solving various geological and geochemical problems due to their unique and chemically coherent behavior. The river sediments are produced by weathering, transportation and deposition. Nesbitt suggested that the rare-earth elements had been mobilized and fractionated during supracrustal alteration of the Torrongo granite, southeastern Australia. Nevertheless, recently, our replicate estimation for REE patterns in sediments revealed that there is nearly no variation in REE patterns. This suggests that invariability of REE patterns in weathering and solidification can be used as a tracer for constraining the provenance of stream sediments. In order to trace the pathway of the river sediments geochemically, based on the REE geochemistry from the river sediments and rocks, we have monitored the REE abundance of stream sediments at branch rivers of the Namhan River in South Korea for three years. The branches studied are Bokhacheon, Shinduncheon and Yanghwacheon. The sediments were divided into coarse （〉300 μm） and fine fractions （〈300 μm）. As a result, we could observe that major element compositions were similar to each other regardless of particle size and sampling date. This suggests that it is difficult to deduce a geochemical difference between river sediments based on major element composition and particle size. The geochemical characteristics of surrounding soils were similar to those of fine river sediments. And the chondrite-normalized REE patterns of most of the fine and coarse sediments in combination with grain sizes and drainage area showed very close relationship with the surrounding rocks. However, some sites showed that there were large variations in REE patterns including total REE abundance and Eu anomaly due to feldspars. This variation trend of REE patterns suggests that changes might have happened in sediment supply for the drainage system in the study area due to floods or large-scale construction.