Early diagenetic behaviour of selenium in freshwater sediments

The vertical distributions of dissolved Se species [Se(IV), Se(VI) and organic Se] and diagenetic constituents [Fe(II) and Mn(II)] were obtained in porewater samples of two Sudbury area lakes (Clearwater and McFarlane). The sedimentary concentration profiles of total Se, Se species bound to Fe–Mn oxyhydroxides and to organic matter, and of elemental Se were also determined along with the concentrations of Fe, Mn and S in different extractable fractions. Results indicated that the concentrations of total dissolved Se in porewater samples were very low, varying from around 2.0 nM to a maximum level of 6.5 nM, while the concentrations of total Se species in the solid phase varied between 2 and 150 nmol/g on a dry weight basis. The two lakes showed striking differences in the presence of Se(IV) and Se(VI) at the sediment–water interface (SWI). In Clearwater Lake, Se(VI) was present at this interface and Se(IV) was not detectable, whereas the opposite was found in McFarlane Lake. This suggests that reducing conditions might have existed near the SWI of McFarlane Lake at the sampling time; this hypothesis was confirmed by several other measured chemical parameters. The profiles of total dissolved Se of both lakes suggest upward and downward diffusion of dissolved Se species along the concentration gradients. Assuming that no precipitation occurred at the SWI, the fluxes of dissolved Se species across the SWI in Clearwater and McFarlane lakes were estimated to be 0.108 and 0.034 nmol cm⁻² a⁻¹, respectively. These values do not include the possible losses of volatile Se species due to microbial methylation. In the reducing sediments of both lakes, the formation of elemental Se and pyritic Se were found to be important mechanisms for controlling the solubility of Se in this environment. The main geochemical processes involving Se identified in this study are: the adsorption of Se onto Fe–Mn oxyhydroxides at or near the SWI, the release of adsorbed Se by the reduction of the same oxyhydroxides and the mineralization of organic matter, and the removal of Se from porewaters to form elemental Se and a S mineral phase such as Se–pyrite or pure ferroselite.     

Dissolved Boron in the Tapi,Narmada and the Mandovi Estuaries,the Western Coast of India: Evidence for Conservative Behavior

The concentrations of dissolved boron have been measured during different seasons in three estuaries, the Tapi, Narmada and the Mandovi situated on the western coast of India, to investigate its geochemical behavior and inputs from the localized anthropogenic pressures of industrial effluents and sewage discharge. The measured boron concentrations in these estuaries (except the Tapi during non-monsoon) at salinity ≤0.1 fall in a narrow range?～?2–4 μmol/kg (average B?～?2.4?±?0.8 μmol/kg) within the reported wide range?～?0.1–18.6 μmol/kg for global rivers. The much higher estimate of boron concentration in the Tapi River during non-monsoon is attributed to its possible additional supply from the sewage and/or industrial effluents discharged along the river course. During monsoon, the rains seem to be a significant source of dissolved boron to all the three rivers. The distribution of dissolved boron in each estuary exhibits a conservative behavior during the seasons sampled suggestive of no measurable addition or removal of boron in the estuarine region. The orders of magnitude differences in boron concentration between the river waters and seawater, and the conservative behavior of dissolved boron indicate that its major contributor to the estuaries sampled is seawater.     

Trace metals and dissolved organic carbon in an estuary with restricted river flow and a brown tide bloom

This study was designed to establish the distributions of trace metals (Cd, Co, Cu, Ni, Pb, and Zn), dissolved organic carbon (DOC), and inorganic nutrients (PO₄ and H₄SiO₄) in the water column of the small, relatively pristine Peconic River estuary. We were also able to examine the effects of a harmful microalgal bloom, known as the brown tide, which occurred in the area during our study. Because river inflow to the Peconic estuary is restricted by a small dam at the head of the estuary, direct evaluation of the relative importance of riverine inputs on estuarine metal distributions was possible. The simultaneous analyses of geochemical carrier metals (Al, Fe, and Mn), an indicator of sewage (Ag), and other ancillary parameters (e.g., suspended particulate matter, dissolved O₂, chlorophylla) were used to describe the major processes controlling metal concentrations in the dissolved phase. The trace metal distributions indicated two distinct biogeochemical regimes within the estuary: an anthropogenically perturbed region with high metal levels (e.g., Ag, 165 pM; Cu, 51 nM; Zn, 57 nM) at the head (Flanders Bay), and a larger outer region with relatively low metal concentrations. The very similar distributions of some metals (e.g., Mn, Ni) in the Peconic estuary compared to those in estuaries having much higher river flow demonstrated the dominant role of internal processes (e.g., diagenetic remobilization) in controlling these metal patterns. An inverse relationship between dissolved Fe and DOC with cell counts of the brown tide microalgaeAureococcus anophagefferens in our field study suggested a close association with the bloom, although a similar relationship was observed between dissolved Al and brown tide cell counts, implying that removal of Fe could be due to particle scavenging rather than biological uptake.     

Dissolved inorganic and organic selenium in the Orca Basin

The vertical distributions of Se (IV), Se (VI) and dissolved organic Se have been determined in the oxic and non-sulfide-bearing anoxic zones of the Orca Basin. In the oxic waters, the concentration of Se (IV) increases with depth gradually from 0.25 nmole/kg at the surface to a maximum of 0.46 nmole/kg at 750 m and then decreases with depth to a relatively constant concentration of 0.39 nmole/ kg below 1,230 m. The concentration of Se (VI) is rather uniform in the top 250 m at about 0.24 nmole/ kg. Below 250 m it increases with depth to 0.50 nmole/kg at 1.230 m, and it stays relatively constant below this depth. The concentration of organic Se increases from 0.50 nmole/kg at the surface to 1.39 nmole/kg at 78 m. A pronounced broad maximum of organic Se exists between 78 and 250 m. The concentration decreases with depth below 250 m, dropping sharply between 250 and 380 m and more gradually at greater depths. It becomes undetectable at 1,230 m. Organic Se is the dominant species above 250 m. Se (IV) is the most abundant between 250 and 1,000 m while Se (VI) becomes the dominant species below 1,000 m. The distributions of these three species can be explained by the biological uptake of Se in the surface waters and the multi-step regeneration of Se from biogenic particles at greater depths. In suboxic waters at the oxic-anoxic interface, the concentration of Se (IV) increases while that of Se (VI) decreases reflecting a change in redox conditions in the environment. In the anoxic brine, the concentration of Se (IV) is around 0.25 nmole/kg while Se (VI) is undetectable. The concentration of organic Se increases sharply in the suboxic waters and reaches 2.6 nmole/kg in the anoxic brines probably as a result of the decomposition of organic matter and/or a diffusive flux from the underlying sediment.     

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.     

Accumulation and speciation of selenium in evaporation basins in California,USA

The accumulation of selenium in evaporation basins (or ponds) in the San Joaquin Valley, California is of a great concern due to its potential hazards to environments. In this study, the accumulation, speciation and concentrations of Se were examined in waters as well as sediments in a system of the evaporation ponds. A significant decrease in the total dissolved Se concentration in Cell 1 in which drainage water with higher Se concentration was pumped from Inlet Channels indicated that the immobilization of Se was active in the Cell 1 and resulted in the higher Se concentration in sediments compared to the terminal cell such as Cell 9. The percentage of reduced Se species such as selenite [Se(IV)] and org-Se of total Se in drainage waters was also found increased in Cell 1 compared to Inlet Channels. The total dissolved Se concentrations in water along flow paths from Cell 1 were relatively constant except for terminal cells such as Cells 9 and 10, which showed higher total dissolved Se concentrations due to evapoconcentration. The percentage of reduced Se forms of total Se was inversely proportional to the percentage of Se(VI) depending on the redox condition of evaporation ponds along the flow paths. Sequential extractions of Se species in sediments indicated that organic associated Se and elemental Se were prevalent forms in sediments in the ponds system. The higher concentrations of elemental Se and organic associated Se in sediments in Cell 1 indicated that the immobilization of Se was active in the sediments compared to Cell 9, while the percentage of both fractions of total Se in sediments in Cells 1 and 9 was relatively constant. The organic materials from algae might provide carbon sources for Se reduction and Se sink in sediments in its elemental and organic associated forms.     

Surface complexation effects on phosphate adsorption to ferric iron oxyhydroxides along pH and salinity gradients in estuaries and coastal aquifers

Non-conservative behavior of dissolved inorganic phosphate (DIP) in estuaries is generally ascribed to desorption from iron and aluminum (hydr)oxides with increasing salinity. Here, we assess this hypothesis by simulating the reversible adsorption of phosphate onto a model oxide (goethite) along physico-chemical gradients representative of surface and subsurface estuaries. The simulations are carried out using a surface complexation model (SCM), which represents the main aqueous speciation and adsorption reactions of DIP, plus the ionic strength-dependent coulombic interactions in solution and at the mineral-solution interface. According to the model calculations, variations in pH and salinity alone are unlikely to explain the often reported production of DIP in surface estuaries. In particular, increased aqueous complexation of phosphate by Mg²⁺ and Ca²⁺ ions with increasing salinity is offset by the formation of ternary Mg-phosphate surface complexes and the drop in electrical potential at the mineral-water interface. However, when taking into account the downstream decrease in the abundance of sorption sites, the model correctly simulates the observed release of DIP in the Scheldt estuary. The sharp increase in pH accompanying the admixing of seawater to fresh groundwater should also cause desorption of phosphate from iron oxyhydroxides during seawater intrusion in coastal aquifers. As for surface estuaries, the model calculations indicate that significant DIP release additionally requires a reduction in the phosphate sorption site density. In anoxic aquifers, this can result from the supply of seawater sulfate and the subsequent reductive dissolution of iron oxyhydroxides coupled to microbial sulfate reduction.     

Origin of the difference in the distribution behavior of tellurium and selenium in a soil-water system

The distribution behavior of tellurium (Te) between soil and water in a synthetic soil-water system was studied coupled with the speciation of Te both in soil and water phases by using X-ray absorption fine structure (XAFS) spectroscopy and a high-performance liquid chromatography connected to an ICP-MS (HPLC-ICP-MS), respectively. The results were compared with a similar data set for Se, which was simultaneously obtained in this study. The oxidation states and host phases of Te and Se in the soil samples were given by XAFS, while the oxidation states in water were given by HPLC-ICP-MS. It was found that both Te and Se in soil are mainly associated with Fe(III) hydroxides under oxic conditions. From the EXAFS analyses, the outer-sphere complex is important for the Se(VI) sorbed on Fe(III) hydroxides in soils, while Se(IV), Te(IV), and Te(VI) form inner-sphere complexes. Under reducing condition, it was found that Te(0) and Se(0) species were formed and that Se was more readily reduced to Se(0) than Te, as is predicted from their Eh-pH diagrams. The reduction process from hexavalent to zerovalent species was different between Se and Te, that is, the direct reduction from Se(VI) to Se(0) was observed for Se, while Te was reduced stepwise from Te(VI) to Te(0) via Te(IV). In terms of the distribution between soil and water, Se distribution to water was much higher than that of Te under wide redox conditions. For Se, selenate is the predominant species in water even under reducing condition due to the much higher solubility of Se(VI) than Se(IV). Furthermore, a much smaller distribution of Te in water was primarily due to the larger affinities of Te(IV) and Te(VI) to Fe(III) hydroxides than Se(VI), which originates from the formation of the inner-sphere complexes of Te(IV) and Te(VI) to Fe(III) hydroxides.     

Comparison of controlling mechanisms of flocculation processes in estuaries

During estuarine mixing, dissolved metals come into the particulate phase due to the flocculation processes. Such processes are biologically vital. In the present study, controlling mechanisms of elemental flocculation during estuarine mixing in northern and southern estuaries of Iran in relation to the various physical and chemical parameters of waters have been compared. Except for zinc and lead, for other studied elements in Minab River, water flocculate at higher rates in comparison with the rivers flowing into the Caspian Sea. Redox potential might have negative effect on flocculation process in Minab Estuary. Contrary to rivers flowing into the Caspian Sea, in Minab River elemental flocculation is governed by dissolved organic carbon and it shows a non-liner and conservative behavior during estuarine mixing which implies that dissolved organic carbon originates from terrigenous source. The results also shows that maximum removal of elements occurs in lower salinities (1.5 to 5.8 ‰) for the rivers in North of Iran and 3.3 to 11.4 ‰ for Minab River in South of Iran. Flocculation of studied metal in different rivers results in reduction of overall metal pollution load by various percentages. The initial metal contents on river water and mean discharge of river might lead to higher flocculation rates.     

Seasonal cycle and mass balance of cadmium in an estuary with an agricultural catchment: The Morlaix River estuary (Brittany,France)

Cadmium (Cd) variations were investigated over an annual cycle (12 surveys between February 1998–January 1999) in the Morlaix estuary (Brittany, France) in both the water column and the benthic compartment in relation to hydrological conditions. The drainage basin of the Morlaix River estuary is predominantly agricultural in character. Dissolved Cd concentrations in the water column varied from 0.04 to 0.48 nM. Particulate Cd concentrations ranged from 1 to 64 nmol g⁻¹. These concentrations reach levels commonly observed in estuaries affected by heavy industrial activities. Extensive agricultural activities in the drainage basin may be responsible for Cd levels above pristine conditions. Metal concentrations varied significantly over the seasonal cycle and the dissolved fraction exhibited high values in summer months. Particulate concentrations were always lowest during this season. In the benthic compartment, Cd concentrations in surface sediment varied from 0.4 to 5.0 nmol g⁻¹ and from 0.2 to 5.0 nM in porewaters. Concentrations in sediment were slightly affected by Cd contamination and temporal changes were important over the seasonal cycle. The variations seem to be controlled by the succession of sedimentation and erosion processes, which are tightly linked to seasonal changes in river discharge. A box model was constructed based on known Cd sources and sinks in the estuary. Cd is chiefly brought into the estuary by the Morlaix River and accumulates within the estuary. The accumulation within the estuary represents from 6.3 to 7.2 kg yr⁻¹.     

Dissolved sulfides in the oxic water column of San Francisco Bay,California

Trace contaminants enter major estuaries such as San Francisco Bay from a variety of point and nonpoint sources and may then be repartitioned between solid and aqueous phases or altered in chemical speciation. Chemical speciation affects the bioavailability of metals as well as organic ligands to planktonic and benthic organisms, and the partitioning of these solutes between phases. Our previous, work in south San Francisco Bay indicated that sulfide complexation with metals may be of particular importance because of the thermodynamic stability of these complexes. Although the water column of the bay is consistently well-oxygenated and typically unstratified with respect to dissolved oxygen, the kinetics of sulfide oxidation could exert at least transient controls on metal speciation. Our initial data on dissolved sulfides in the main channel of both the northern and southern components of the bay consistently indicate submicromolar concenrations (from <1 nM to 162 nM), as one would expect in an oxidizing environment. However, chemical speciation calculations over the range of observed sulfide concentrations indicate that these trace concentrations in the bay water column can markedly affect chemical speciation of ecologically significant trace metals such as cadmium, copper, and zinc.     

Biodegradation of riverine dissolved organic carbon in five estuaries of the southeastern United States

The biological turnover of riverine dissolved organic carbon (DOC) discharged into five southeastern United States estuaries was examined in long-term respiration bioassays. Measures of bacterial oxygen consumption indicated surprisingly large differences in the inherent biodegradability of DOC among the five estuaries, despite their close geographic proximity. Differences of up to 13-fold in biodegradation rates were also found temporally within a single estuary. For most of the southeastern United States estuaries, measured rates of riverine DOC biodegradation were low relative to rates reported for other freshwater and marine environments. This was particularly true for the coastal plain (“blackwater”) rivers that contribute about 35% of the riverine DOC exported to coastal marine environments in this region; extrapolation of biodegradation rates to the adjacent continental shelf predict biodegradation of a maximum of 11% of exported blackwater DOC within the estuary-shelf system (with transit times of up to 140 d). DOC from Piedmont rivers was more biologically labile, with maximum losses of 30% predicted within the estuary and adjacent shelf. Short exposures to natural sunlight increased the lability of the riverine DOC and enhanced biodegradation rates by over 3-fold in some cases, although significant inter-estuary differences in susceptibility of riverine DOC to photolysis were also evident. *** DIRECT SUPPORT *** A01BY085 00007     

Role of Suspended Particulate Matter in Regulating the Behavior of Dissolved Uranium in the Yellow River Estuary

In order to examine the mixing behavior of dissolved uranium (U) in estuaries under different suspended particulate matter (SPM) regimes, three laboratory-based experiments were conducted by mixing seawater with river water containing different concentrations of SPM. Comparing this study with other field and laboratory-based experiments, dissolved U behaved differently depending upon the concentration of SPM. When SPM concentrations are >?0.8 g/L in the Yellow River, desorption/dissolution of U from SPM becomes predominant and dissolved U is enriched relative to the theoretical mixing line. However, when SPM concentrations are <?0.8 g/L, dissolved U behaves conservatively with some extent of removal during estuarine mixing. ²³⁴U/²³⁸U activity ratios were somewhat constant showing no measurable isotopic fractionation during physical mixing and U sorption/desorption to/from particles. Addition of dissolved ²³⁸U desorbed/dissolved from SPM during the annual Yellow River water-sediment regulation scheme (Jun 30th–Jul 14th, 2014) was estimated at 6.4?×?10¹¹ dpm, about 9% of the total riverine flux of dissolved ²³⁸U during that same period. This study represents a contribution to studies of dissolved U in muddy rivers and estuaries throughout the world. Results reported here provide not only a perspective to better estimate U flux from rivers to the ocean but also new insights into better understanding its estuarine mixing behavior and controlling factors.     

The relationships among man’s activities in watersheds and estuaries: A model of runoff effects on patterns of estuarine community metabolism

Activities of man in rivers and their watersheds have altered enormously the timing, magnitude, and nature of inputs of materials to estuaries. Despite an awareness of large-scale, long-term changes in river-estuarine watersheds, we do not fully understand the consequences to estuarine ecosystems of these activities. Deforestation, urbanization, and agriculturalization have changed the timing and nature of material inputs to estuaries. Conversion of land from forest to almost any other land use promotes overland flow of storm runoff; increases the timing, rate and magnitude of runoff; and increases sediment, organic matter, and inorganic nutrient export. It has been estimated that total organic carbon levels in rivers have increased by a factor of 3–5 over natural levels. Man’s activities have also changed the magnitude of particulate organic carbon relative to dissolved organic carbon export and the lability of the organic matter. Historically, rivers and streams had different features than they do today. Two of man’s activities that have had pronounced effects on the timing and quality of river water are channelization and damming. Agricultural drainage systems, channelized and deepened streams, and leveeing and prevention of overbank flooding have had the combined effect of increasing the amplitude and rate of storm runoff, increasing sediment load, increasing nutrient delivery downstream, and decreasing riparian wetland productivity. Dams on the other hand have altered natural discharge patterns and altered the downstream transfer of sediments, organic matter, and nutrients. Patterns of estuarine community metabolism are sensitive to variations, in the timing, magnitude, and quality of material inputs from watersheds. The autotrophic-heterotrophic nature of an estuary is determined by three primary factors: the ratio of inorganic to organic matter inputs, water residence time, and the overall lability of allochthonous organic matter inputs. A simulation model is used to explore the effects of man’s activities in watersheds on the spatial patterns of production and respiration in a generalized estuarine system. Examined are the effects of variations in the ratios of inorganic and organic nitrogen loading, the residence time of water in the estuary, the degradability of allochthonous organic matter, and the ratio of dissolved to particulate organic matter inputs. Simulations suggest that the autotrophic-heterotrophic balance in estuaries is more sensitive to variations in organic matter loading than inorganic nutrient loading. Water residence time and flocculation-sedimentation of organic matter are two physical factors that most effect simulated spatial patterns of metabolism in estuaries.     

Accumulation of terrestrial organic carbon on an active continental margin offshore southwestern Taiwan: Source-to-sink pathways of river-borne organic particles

Sediment samples (213 sites) collected from the tectonic-active continental margin, offshore southwestern Taiwan were analyzed for grain sizes, organic carbon, nitrogen and carbon isotopic composition to obtain mass accumulation rate of terrestrial organic carbon and carbon budget to evaluate fate of terrestrial organic carbon from small mountainous rivers on the continental margin offshore southwestern Taiwan. Terrestrial organic carbon accumulation rates range from 0.29 to 45.6 g C m⁻² yr⁻¹ with a total accumulation budget of 0.063 Mt yr⁻¹, which accounts for less than 13% of total river particulate organic carbon loads exported from the adjacent rivers, the Gaoping (a.k.a., Kaoping), Erhjen and Tsengwen rivers. This low burial efficiency of terrestrial organic carbon demonstrated that a majority of river-borne particles together with organic materials was moved away from the study area.For the river-borne particles from the Gaoping river, a pair of depocenters in the upper slope flanking the Gaoping submarine canyon are the locations where the maximum TC_org accumulation rate were observed which hold up to 45% (0.016 Mt yr⁻¹) of the calculated accumulation found in the study region. On the other hand, the occurrence of higher-fraction terrestrial organic carbon in the upper and middle Gaoping submarine canyon suggests that a majority of particulate organic carbon of the Gaoping river was transported directly into the deep-sea basin through the Gaoping submarine canyon. Our results demonstrated that active margin with narrow shelf and slope is not an efficient sink for the large amount of terrigenous organic carbon supplied by the small rivers, but, a transient environment for these river derived particles.     

Rare earth elements (REE) of dissolved and suspended loads in the Xijiang River, South China

The Xijiang River is the main channel of the Zhujiang (Pearl River), the second largest river in China in terms of water discharge, and flows through one of the largest carbonate provinces in the world. The rare earth element (REE) concentrations of the dissolved load and the suspended particulate matter (SPM) load were measured in the Xijiang River system during the high-flow season. The low dissolved REE concentration in the Xijiang River is attributed to the interaction of high pH and low DOC concentration. The PAAS-normalized REE patterns for the dissolved load show some common features: negative Ce anomaly, progressively heavy REE (HREE) enrichment relative to light REE (LREE). Similar to the world’s major rivers the absolute concentration of the dissolved REE in the Xijiang River are mainly pH controlled. The degree of REE partitioning between the dissolved load and SPM load is also strongly pH dependent. The negative Ce anomaly is progressively developed with increasing pH, being consistent with the oxidation of Ce (III) to Ce (IV) in the alkaline river waters, and the lack of Ce anomalies in several DOC-rich waters is presumably due to both Ce (III) and Ce (IV) being strongly bound by organic matter. The PAAS-normalized REE patterns for the dissolved load and the SPM load in rivers draining the carbonate rock area exhibit middle REE (MREE) enrichment and a distinct maximum at Eu, indicating the preferential dissolution of phosphatic minerals during weathering of host lithologies. Compared to the Xijiang River waters, the MREE enrichment with a maximum at Eu disappeared and light REE were more depleted in the South China Sea (SCS) waters, suggesting that the REE sourced from the Xijiang River must be further fractionated and modified on entering the SCS. The river fluxes of individual dissolved REE introduced by the Xijiang River into the SCS vary from 0.04 to 4.36 × 10⁴ mol a⁻¹.     

恩施渔塘坝富硒碳质岩石中硒的形态分析

湖北恩施渔塘坝是中国人群硒中毒爆发性流行的地区,也是恩施较为典型的高硒地区之一。其北部出露的富硒碳质岩石,通常认为是渔塘坝硒的主要来源。采用7步连续化学浸提技术,将富硒碳质岩石中硒分为水溶态、可交换态、有机态、元素态、酸性提取态、硫化物／硒化物态和残渣态硒,使用氢化物-原子荧光法测定了岩石总硒和硒形态。结果表明,碳质页岩和碳质硅质岩中硒主要以有机态、硫化物／硒化物态和可交换态硒为主,碳质泥岩中硒以有机态、元素态和硫化物／硒化物态硒为主。碳质泥岩中的水溶态硒显著低于碳质页岩和碳质硅质岩中的水溶态硒,但元素态硒的比例显著高于后两者,说明碳质泥岩是富硒碳质岩层中硒易于富集的场所。富硒碳质岩中的可利用态硒主要以Se^4＋为主,而非是Se^6＋和有机硒。可交换态和有机结合态硒中Se^4＋与岩石总硒的显著正相关关系表明,Se^4＋离子的分布影响着岩石总硒,有机质与粘土在硒富集的地球化学过程中承担了重要作用。     

A field experiment testing for correspondence between trace elements in otoliths and the environment and for evidence of adaptation to prior habitats

Site-specific variation in the trace element composition of fish otoliths can be used to identify fish to source, but the mechanisms controlling elemental composition are poorly understood. Environmental influences on the deposition of barium (Ba), copper (Cu), manganese (Mn), and strontium (Sr) in the otoliths of mudsuckers (Gillichthys mirabilis) were tested using a reciprocal field transplant experiment, in which fish from 3 estuaries were transplanted to each of the 3 estuaries. Fish originating from the 3 estuaries showed no differences in otolith chemistry that might reflect acclimation to past conditions in their home estuary or genetic differences among populations, which simplifies the interpretation of otolith chemistry. Cu and Mn concentrations in otoliths differed according to the site of transplant. Cu in otoliths showed the same pattern of difference among estuaries as did Cu in sediments, but there was no correspondence between Cu in otoliths and dissolved Cu. Ranked differences among estuaries in otolith Mn matched the ranking of estuary-specific differences in dissolved Mn, and there was no correspondence between the concentration of Mn in otoliths and sediments. Fish transplanted to different estuaries showed no differences in otolith concentrations of Ba or Sr, and the concentrations of Ba and Sr in the water column showed a similar lack of difference among estuaries. This study provides field evidence supporting the conclusion that the elemental composition of otoliths reflects environmental conditions to which fish have been recently exposed, but whether that correlation is with trace elements in the sediment or water column can vary.     

Organic complexation of rare earth elements in natural waters: Evaluating model calculations from ultrafiltration data

The Stockholm Humic Model (SHM) and Humic Ion-Binding Models V and VI were compared for their ability to predict the role of dissolved organic matter (DOM) in the speciation of rare earth elements (REE) in natural waters. Unlike Models V and VI, SHM is part of a speciation code that also allows us to consider dissolution/precipitation, sorption/desorption and oxidation/reduction reactions. In this context, it is particularly interesting to test the performance of SHM. The REE specific equilibrium constants required by the speciation models were estimated using linear free-energy relationships (LFER) between the first hydrolysis constants and the stability constants for REE complexation with lactic and acetic acid. Three datasets were used for the purpose of comparison: (i) World Average River Water (Dissolved Organic Carbon (DOC) = 5 mg L⁻¹), previously investigated using Model V, was reinvestigated using SHM and Model VI; (ii) two natural organic-rich waters (DOC = 18-24 mg L⁻¹), whose REE speciation has already been determined with both Model V and ultrafiltration studies, were also reinvestigated using SHM and Model VI; finally, (iii) new ultrafiltration experiments were carried out on samples of circumneutral-pH (pH 6.2-7.1), organic-rich (DOC = 7-20 mg L⁻¹) groundwaters from the Kervidy-Naizin and Petit-Hermitage catchments, western France. The results were then compared with speciation predictions provided by Model VI and SHM, successively. When applied to World Average River Water, both Model VI and SHM yield comparable results, confirming the earlier finding that a large fraction of the dissolved REE in rivers occurs as organic complexes This implies that the two models are equally valid for calculating REE speciation in low-DOC waters at circumneutral-pH. The two models also successfully reproduced ultrafiltration results obtained for DOC-rich acidic groundwaters and river waters. By contrast, the two models yielded different results when compared to newly obtained ultrafiltration results for DOC-rich (DOC > 7 mg L⁻¹) groundwaters at circumneutral-pH, with Model VI predictions being closer to the ultrafiltration data than SHM. Sensitivity analysis indicates that the “active DOM parameter” (i.e., the proportion of DOC that can effectively complex with REE) is a key parameter for both Model VI and SHM. However, a survey of ultrafiltration results allows the “active DOM parameter” to be precisely determined for the newly ultrafiltered waters studied here. Thus, the observed discrepancy between SHM predictions and ultrafiltration results cannot be explained by the use of inappropriate “active DOM parameter” values in this model. Save this unexplained discrepancy, the results presented in this study demonstrate that both Model VI and SHM can provide reliable estimates of REE speciation in organic-rich waters. However, it is essential to know the proportion of DOM that can actively complex REE before running these two speciation models.     

The aquatic chemistry of rare earth elements in rivers and estuaries

Laboratory experiments were carried out to determine how pH, colloids and salinity control the fractionation of rare earth elements (REEs) in river and estuarine waters. By using natural waters as the reaction media (river water from the Connecticut, Hudson and Mississippi Rivers) geochemical reactions can be studied in isolation from the large temporal and spatial variability inherent in river and estuarine chemistry. Experiments, field studies and chemical models form a consistent picture whereby REE fractionation is controlled by surface/solution reactions. The concentration and fractionation of REEs dissolved in river waters are highly pH dependent. Higher pH results in lower concentrations and more fractionated composition relative to the crustal abundance. With increasing pH the order of REE adsorption onto river particle surfaces is LREEs > MREEs > HREEs. With decreasing pH, REEs are released from surfaces in the same order. Within the dissolved (<0.22 µm) pool of river waters, Fe-organic colloids are major carriers of REEs. Filtration through filters and ultrafilters with progressively finer pore sizes results in filtrates which are lower in absolute concentrations and more fractionated. The order of fractionation with respect to shale, HREEs > MREEs > LREEs, is most pronounced in the solution pool, defined here as <5K and <50K ultrafiltrates. Colloidal particles have shale-like REE compositions and are highly LREE enriched relative to the REE composition of the dissolved and solution pools. The addition of sea water to river water causes the coagulation of colloidal REEs within the dissolved pool. Fractionation accompanies coagulation with the order of sea water-induced removal being LREEs > MREEs > HREEs. While the large scale removal of dissolved river REEs in estuaries is well established, the release of dissolved REEs off river particles is a less studied process. Laboratory experiments show that there is both release and fractionation of REEs when river particles are leached with seawater. The order of sea water-induced release of dissolved REE(III) (LREEs > MREEs > HREEs) from Connecticut River particles is the same as that associated with lowering the pH and the same as that associated with colloidal particles. River waters, stripped of their colloidal particles by coagulation in estuaries, have highly evolved REE composition. That is, the solution pool of REEs in river waters are strongly HREE-enriched and are fractionated to the same extent as that of Atlantic surface seawater. This strengthens the conclusions of previous studies that the evolved REE composition of sea water is coupled to chemical weathering on the continents and reactions in estuaries. Moreover, the release of dissolved Nd from river particles to sea water may help to reconcile the incompatibility between the long oceanic residence times of Nd (7100 yr) and the inter-ocean variations of the Nd isotopic composition of sea water. Using new data on dissolved and particle phases of the Amazon and Mississippi Rivers, a comparison of field and laboratory experiments highlights key features of REE fractionation in major river systems. The dissolved pool of both rivers is highly fractionated (HREE enriched) with respect to the REE composition of their suspended particles. In addition, the dissolved pool of the Mississippi River has a large negative Ce-anomaly suggesting in-situ oxidation of Ce(III). One intriguing feature is the well developed maximum in the middle REE sector of the shale normalized patterns for the dissolved pool of Amazon River water. This feature might reflect competition between surface adsorption and solution complexation with carbonate and phosphate anions.