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1.
River water (Water of Luce, Scotland) is used in laboratory experiments designed to investigate physical and chemical properties of Fe. Mn, Cu, Ni, Co, Cd and humic acids in riverine and estuarine systems. Using NaCl, MgCl2 and CaCl2 as coagulating agents, coagulation of dissolved (0.4 μm filtered) Fe, Cu, Ni, Cd and humic acids increases in a similar matter with increasing salt molarily: Ca2+ is the most dominant coagulating agent. Removal by coagulation with Ca2+ at seawater concentrations ranges from large (Fe-80%. HA-60%, Cu-40%) to small (Ni, Cd-15%) to essentially nothing (Cd, Mn-3%). Destabilization of colloids is the indicated mechanism. Solubility-pH measurements show that between a pH of 3 and 9, Fe, Cu, Ni, Mn, Co and Cd are being held in the dissolved phase by naturally occurring organic substances. Between pH of 2.2 and 1.2 a large proportion of dissolved Fe, Cu. Ni and Cd (72, 35,44 and 36% respectively) is precipitated along with the humic acids; in contrast, Mn and Co show little precipitation (3%). Adsorption-pH experiments, using unfiltered river water spiked with Cu, indicate that adsorption of Cu onto suspended particles is inhibited to a large extent by the formation of dissolved Cu-organic complexes.The experimental results demonstrate that solubilities and adsorption properties of certain trace metals in freshwaters can be opposite to those observed with artificial solutions or predicted with chemical models. Interaction with organic substances is a critical factor. 相似文献
2.
I. M. Varentsov N. V. Bakova Yu. P. Dikov T. S. Gendler R. Giovanoli 《Mineralium Deposita》1979,14(3):281-296
Experiments on the sorption of dissolved Ni, Co, Mn, Fe from seawater by Mn3O4 reveal a sequence of reactions taking place: Ion exchange, hydrolysis, then autocatalytic oxidation and layer formation on the interface. The composition of the new compounds depends on the kinetics of i) sorption, and ii) interface oxidation. The highest oxidized Me ions accumulate at low sorption rates, i. e. when sorption does not inhibit interface oxidation: 60% Mn4+, 30% Ni3+ & 30% Co3+ are a representative example for that layer type. Iron is present in this layer as amorphous FeOOH·xH2O according to Mössbauer spectra. Specific for the Me sorption by Mn3O4 is the interaction of Ni & Co with Mn2+ and Mn3+ of the sorbent lattice. Mn is found in the solute phase equivalent to 16, 14% of the adsorbed Co or 17, 96% of the adsorbed Ni. These results confirm the earlier presented model on the transition metal accumulation in recent basins as taking place in distinct stages with interface autocatalysis for the Me oxidation playing the main role. 相似文献
3.
Fine sludges were collected from five filtration plants, and the partitioning of ten metals (Ag, Cd, Mn, Zn, Pb, Cu, Sn, Co, Ni, and Fe) in them was determined by selective leaching techniques. (1) The available amounts, which shows the total of each metal leached between 1 M CH3COONH4 and 30 percent H2O2, for Ag, Cd and Mn, ranged from 51 to 98 percent for five sludges. (2) The available amounts for Zn, Pb, Cu, and Sn were 47–92 percent for five sludges. (3) The most important fraction for Co, Ni, and Fe, except the Inagawa sludge, which is markedly polluted by organic matter, was the crystalline particle. Therefore, the above metals, except Co, Ni, and Fe, are thought to be enriched on ion-exchangeable sites, organic matter, hydrous Fe/Mn oxides, and sulfides in fine sludges. 相似文献
4.
Mobility of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric O2: an experimental study 总被引：1，自引：0，他引：1
Mats Åström 《Environmental Geology》1998,36(3-4):219-226
The major aim was to increase our knowledge on the behaviour of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained
sediments exposed to atmospheric oxygen. Samples of this type of sediment collected in a previous investigation at eight sites
in western Finland were digested in HClO4-HNO3-HCl-HF at 200 °C and in HCl:HNO3:H2O at 95 °C (aqua regia), and subjected to extractions with ammonium acetate and hydrogen peroxide. Metals and S in the leachates
were determined with ICP-AES. The results of the chemical analyses are compared with previously reported experimental data.
The concentrations of Al and Fe in the sulphide-bearing fine-grained sediments are about 7% and 5%, respectively. Of the trace
metals studied, Mn is most abundant followed in decreasing order by V>Cr>Ni>Cu>Co. On oxidation of the sediments, high proportions
of Co, Mn and Ni, intermediate proportions of Cu but low proportions of Fe, Al, Cr and V are released. The extent of the release
of a metal on oxidation is controlled either by (1) the level to which the pH of the sediments drops on oxidation (Al, Cu,
Cr, V), (2) the amount of the metal associated with easily reduced phases (metal sulphides) in the sediments (Ni, Co) or (3)
the sum of the amount associated with reduced phases and adsorbed on soil compounds (Mn). No control of the release of Fe
on oxidation of the sediments was identified. Based on the results of the study it is argued that artificial drainage and
the subsequent oxidation of sulphide-bearing sediments will result in extensive leaching of Co, Mn and Ni, moderate leaching
of Cu and limited leaching of Cr and V into drainages. The major elements, Fe and Al, have the potential to be mobilised and
leached in large amounts, though the proportions mobilised/leached will remain low. It is suggested that the identification
of sulphide-bearing sediments with a high potential of metal release should be based on determination of metals in easily
mobilised reduced compounds (dissolved e.g. in H2O2) and of the level to which the pH of the sediments drops on oxidation.
Received: 16 October 1997 · Accepted: 9 March 1998 相似文献
5.
Harry Sandstrm 《Journal of Geochemical Exploration》1984,21(1-3)
Organic-rich stream sediments, a widely used material in geochemical prospecting in Finland, were investigated by analyzing Mn, Fe, Co, Ni, Cu and Zn after a series of selective extractions.Forty-seven organic-rich stream-sediment samples were collected in the vicinity of a sulphide mineralization in Talvivaara, eastern Finland. Loss on ignition of the samples at 500°C was 20–95%. pH of the samples, measured in the water pressed from the samples, was 3.4–6.2 with a mean of 4.2.The < 0.5 mm grain-size fraction was subjected to a sequential extraction as follows: NH4-acetate for exchangeable cations; cold NH2OH·HCl for dissolution of Mn oxides; H2O2 for destruction of organic material; hot NH2OH·HCl for dissolution of Fe oxides; HF/HClO4/aqua regia for dissolving the residue. Each extraction was analyzed by flame AAS for Mn, Fe, Co, Ni, Cu and Zn.Manganese and Co are mostly in exchangeable form and in the residue, while the proportion complexed by the organic components is minimal. Iron and Ni own a lot of exchangeable character although a significant proportion of these elements is complexed by the organic components. Most of Cu is in organic form. Zinc is the element most evenly distributed between extractions. 相似文献
6.
Effects of grazing and livestock exclusion on soil physical and chemical properties in desertified sandy grassland,Inner Mongolia,northern China 总被引：3，自引：1，他引：2
Yuqiang Li Halin Zhao Xueyong Zhao Tonghui Zhang Yulin Li Jianyuan Cui 《Environmental Earth Sciences》2011,63(4):771-783
Heavy grazing is recognized as one of the main causes of vegetation and soil degradation and desertification in the semiarid
Horqin sandy grassland of northern China. Soil physical and chemical properties were examined under continuous grazing and
exclusion of livestock for 8 years in a representative desertified sandy grassland. Exclosure increased the mean soil organic
C, total N, fine sand and silt + clay contents, inorganic C (CaCO3), electrical conductivity, and mineral contents (including Al2O3, K2O, Na2O, Fe2O3, CaO, MgO, TiO2, MnO), microelements (Fe, Mn, Zn, B, Cu, Mo), and heavy metals (Pb, Cr, Ni, As, Hg, Cd, Se), and decreased the coarse sand
content, bulk density, and SiO2 in the top 100 cm of the soil. Livestock exclusion also improved available N, P, K, Fe, Mn, and Cu, exchangeable K+, and the cation exchange capacity, but decreased pH, exchangeable Na+, and available S, Zn, and Mo in the top 20 cm of the soil. The greatest change in soil properties was observed in the topsoil.
The results confirm that the desertified grassland is recovering after removal of the livestock disturbance, but that recovery
is a slow process. 相似文献
7.
Robert H. Carpenter Gene D. Robinson Willis B. Hayes 《Journal of Geochemical Exploration》1978,10(1):75-89
Sequential digestions of Fe-Mn oxide coated boulders collected upstream and downstream from the Magruder mine, Lincoln Co., Georgia, indicate probable partitioning relationships for Zn, Cu, Pb, Co, and Ni with respect to Mn and Fe. Initial digestion with 0.1M hydroxylamine hydrochloride (Hxl) in 0.01M HNO3 selectively dissolyes Mn oxides, whereas subsequent digestion with 1:4 HCl dissolves remaining Fe oxides.The results indicate that partitioning is not constant, but varies systematically with respect to the location of metal-rich waters derived from sulfide mineralization. Upstream from the mineralized zone Zn and Ni are distinctly partitioned to the Fe oxide component and Co and Cu are partitioned to the Mn oxide component. Immediately downstream from the mineralized zone, Mn oxides become relatively more enriched in Zn, whereas Fe oxides are relatively more enriched in Cu, Co, and Ni. Analytical precision for Pb is poor, but available data suggests it is more closely associated with Fe oxides.For routine geochemical surveys utilizing coated surfaces, a one-step digestion method is probably adequate. Parameters useful for detecting sulfide mineralization are metal concentrations normalized to surface area or various ratios (e.g. Zn/(Mn + Fe), Cu/Mn, Pb/Fe). Ratios can be obtained much faster, and at lower analytical costs than conventional analysis of stream sediment. 相似文献
8.
9.
《Applied Geochemistry》2003,18(5):693-710
In experiments of 7 days duration using voltammetric and radiotracer measurement techniques, the role of different particle types in the sorption of dissolved metal species in a disturbed deep-sea bottom seawater system were investigated. Resuspension of oxic to suboxic surface sediment into the bottom water in the deep sea (either by natural events or industrial activities like Mn nodule mining) has been shown to be followed quickly by scavenging of dissolved heavy metals, e.g. released from interstitial water, on the resuspended particles. Compared to other deep-sea particles (like clay minerals, calcite and apatite), Mn and Fe oxides and oxyhydroxides were found to be by far the most important phases in scavenging many dissolved heavy metals. Only Pb was sorbed strongly on all particles used, with highest affinity to carbonate fluorapatite. Caesium+ was significantly scavenged only by clay minerals like illite. The sorption experiments support a simple electrostatic model: Hydrated cations and labile cationic chloro-complexes in seawater like Mn2+, MnCl+, Co2+, Ni2+, Cu2+, Zn2+, Ba2+, and PbCl+, are preferentially adsorbed or ion-exchanged on the negatively charged surfaces of Mn oxides. In contrast, oxyanions and neutrally or negatively charged complexes like HVO42−, MoO42−, HAsO42−, UO2(CO3)22−, and PbCO30 associate with neutral to slightly positive amphoteric Fe oxyhydroxide particles. Metals forming strong chloro-complexes in seawater like Cd (CdCl20), are less readily sorbed by oxides than others. A comparison of the results of voltammetric and radiotracer techniques revealed that after fast sorption within the first hour, isotopic exchange dominated reactions on MnO2-rich particles in the following days. This was especially pronounced for Mn and Co which are bound to the Mn oxide surface via a redox transformation. 相似文献
10.
莫托萨拉铁锰矿床位于西天山阿吾拉勒成矿带东端,研究程度相对薄弱,在矿床成因方面存在热水沉积、沉积-热液改造、胶体化学沉积等争论。本文详细研究了莫托萨拉最上层锰矿及其围岩的矿物组成、结构构造和地球化学特征,并综合前人资料对整个铁锰矿床的成因做了进一步探讨。本研究首次在矿区发现了热液长石岩,其主要由钠长石、钾长石以及少量重晶石、霓石、锌铁黄长石等矿物组成,类似于"白烟型"热水沉积岩。莫托萨拉最上层锰矿主要由锰橄榄石、褐锰矿、红硅锰矿、磁锰铁矿以及少量重晶石、方铁锰矿等矿物组成,发育有典型的热水内碎屑结构,指示其沉积于海底热液喷流口附近。该层锰矿的Al/(Al+Fe+Mn)值很低(0～0.02)、Si/Al值较高(7.9～10.9)、Fe/Ti值很高(428～1353),通过UCC标准化后发现明显富集Zn、Ba、Pb等元素,而Co、Ni、Cu等元素未见富集,以上地球化学特征与现代海底热液成因铁锰沉积物一致。在Fe/Ti-Al/(Al+Fe+Mn)、Si O2-Al2O3、10×(Co+Ni+Cu)-Fe-Mn、100×(Zr+Ce+Y)-15×(Cu+Ni)-(Fe+Mn)/4等判别图中,莫托萨拉的锰矿层和铁矿层样品均落在海底热液沉积区。锰矿层和铁矿层的稀土元素经PAAS标准化后具有明显的Ce负异常、Eu正异常和Y正异常,与现代海底热液成因铁锰沉积物的稀土配分模式非常相似。综合分析本次研究的矿物学、岩石学、地球化学特征以及前人资料,本文认为莫托萨拉铁锰矿床为海相热水沉积成因,成矿与同期海底火山的间歇性活动密切相关,海底热液的化学组分、温度高低和活动强弱都具有明显的脉动性。莫托萨拉矿区铁锰共存但各自独立成矿,且铁锰分离程度较高,这在显生宙沉积型锰矿中独具特色。鉴于前人曾报道莫托萨拉铁矿石中存在菌藻类微生物化石,我们推测,该矿床的铁锰分离过程除了受控于沉积环境的氧化还原条件变化外,微生物的选择性氧化沉淀可能也发挥了重要作用,值得开展深入研究。 相似文献
11.
《Chemie der Erde / Geochemistry》2021,81(4):125789
The Montaña de Manganeso is a manganese vein-type deposit spatially associated with back-arc basin remnants of the Guerrero tectonostratigraphic terrane. The study of major- and trace-element geochemical characteristics of the deposit provides insight into the controls on ore-forming processes within the area. The deposit is characterized by low Co, Cu and Ni abundances, and high Ba (>10,000 ppm) contents and Mn/Fe ratios (<500), typical of hydrothermal Mn deposits. In addition, the low ∑REE abundances (18.7 to 103 ppm), negative Ce anomalies (0.2 to 0.6), and positive Y (1.00 to 2.34) and Eu anomalies (0.6 to 4.4) also suggest a hydrothermal source for the deposit. Discrimination plots involving ∑REE and Zr vs. (Cu + Ni + Co) and Ce/Ce* vs. Nd and Y/Ho further indicate a hydrothermal source in an oxidizing depositional environment. The Mn-Fe-(Ni + Cu + Co), MnO2-MgO-Fe2O3, (Cu/Zn)/Fe2O3 vs. (Zn/Ni)/MnO2 and Na/Mg diagrams display intermediate signatures between marine and terrestrial environments. This suggest that the Montaña de Manganeso deposit is the result of two metallogenic stages: (I) the earliest stage, which involved the formation of Mn oxides by hydrothermal/diagenetic processes in the Arperos back-arc basin during the Cretaceous; and (II) the latest stage took place subsequent to accretion the Guerrero tectonostratigraphic terrane onto the continent and involved the remobilization of the Cretaceous submarine Mn oxides (and associated trace elements) and subsequent redepositation by Tertiary continental hydrothermal activity. 相似文献
12.
《Applied Geochemistry》1998,13(5):607-617
Distribution and forms of transition metals (Ti, Zn, Ni, Co, Mn, Fe, Cu, V and Cr) were investigated in oxidised, partly oxidised and reduced zones of sulphide-bearing fine-grained sediments located in the coastal areas of western Finland. Samples for the analysis and study of vertical distribution of elements were taken from each vertical 10 cm section in pits ranging in depth between 2 and 3 metres, while bulk samples for characterisation of species and forms of metals were taken from 3 zones in each pit: the acid sulphate soil (characterised by acid and oxidising conditions), transition zone (characterised by a steep pH gradient and partly oxidising conditions) and the reduced zone (pH >6). The former samples were digested in aqua regia (3:1:2 HCl:HNO3:H2O), while the latter were digested in aqua regia and hot concentrated acids (HClO4–HNO3–HCl–HF) and were subjected to extractions with acid ammonium acetate, H2O2 and acid ammonium oxalate. Each leachate was analysed for metals with ICP–AES.The vertical variation in the concentrations of Ti were small at all the studied sites indicating that the sediments are homogeneous and that the total losses of other elements from the soil profiles (acid sulphate soil+transition zone) are not extensive. Field observations, extractions with ammonium oxalate, and concentration–variation patterns indicated that Fe-oxide is largely precipitated and retained also in these acid soils. There are, however, indications of redistribution of Fe within the soil profiles. The results also demonstrated that Mn, Ni, Zn, Co and Cu have been lost in considerable amounts from the acid sulphate soils. However, whereas Mn in general has been lost throughout the soil profile, part of the Zn, Ni and Co released in the acid sulphate soils have migrated downward and been reimmobilised in the transition zone immediately above the reduced zone. Also Cu has been lost from the acid sulphate soil, but generally in smaller proportions than Mn, Zn, Ni and Co. Dissolved metal sulphides seem to be major sources of the mobilised metal fractions. A main part of the V and Cr in the sediments are associated with weathering-resistant minerals. These metals are therefore, like Ti, only to a limited extent mobilised by the oxidation of the sulphide-bearing sediments. 相似文献
13.
Geoffrey P. Glasby 《Resource Geology》2010,60(2):212-215
Of the 12 elements enriched in Co-rich Mn crusts from the Afanasiy-Nikitin Seamount in the Equatorial S Indian Ocean, Mn, Fe and Co are enriched by a factor of ~109 compared to their concentrations in seawater whereas Ni and Cu are enriched by a factor of ~107 and the PGE and Au by a factor of ~105 to 107 compared to their concentrations in seawater. The relatively high concentration of Pt in the crusts reflects its occurrence as fine-grained particles in the crusts rather than adsorption of the elements from seawater. 相似文献
14.
The Blue Gem coal bed (Middle Pennsylvanian Westphalian B, Breathitt Formation), has low-ash (with some sample sites having less than 1% ash) and low-sulfur contents through parts of Knox County, Kentucky. Most collection sites exhibit similar vertical elemental trends in ash geochemistry. The relatively high-ash (>1% ash) lower part of the bed displays enrichment in TiO2, Zr, Cr, V and Ni; Co, Zn, Rb and Mn show enrichment at some sites. A low-ash (<1% ash) middle part of the bed displays enrichment in Sr, Ba and CaO; Fe2O3 is enriched in samples with carbonate minerals. The upper part of the bed contains >1% ash and a relative enrichment in SiO2, K2O and Rb and a relative decrease in Cu, Ni, Co, Ba and Mn when compared to the middle part of the bed. Principal components analysis indicates that the samples with an ash content 0.63–1.0% show associations for Ni, Cu, Cr and Co. Samples with between 1.01–2.0% ash display strong element associations that suggest increased clastic sediment contributions (TiO2, Zr, K2O, Rb, SiO2). The low-ash content and the upwards decrease in trace concentrations both suggest that the Blue Gem peat swamp was ombrotrophic through at least a part of its geologic history. 相似文献
15.
《Applied Geochemistry》1998,13(2):213-233
Porewater concentration profiles were determined for Fe, trace elements (As, Cd, Co, Cu, Mn, Ni, Pb, Zn), sulfide, SO4 and pH in two Canadian Shield lakes (Chevreuil and Clearwater). Profiles of pyrite, sedimentary trace elements associated with pyrite and AVS were also obtained at the same sites. Thermodynamic calculations are used, for the anoxic porewaters where sulfide was measured, to characterize diagenetic processes involving sulfide and trace elements and to illustrate the importance of sulfide, and possibly polysulfides and thiols, in binding trace elements. The ion activity products (IAP) of Fe sulfide agree with the solubility products (Ks) of greigite or mackinawite. For Co, Ni and Zn, IAP values are close to the KS values of their sulfide precipitates; for Cu and Pb, IAP/Ks indicate large oversaturations, which can be explained by the presence of other ligands (not measured) such as polysulfides (Cu) and thiols (Pb). Cobalt, Cu, Ni and Zn porewater profiles generally display a decrease in concentration with increasing ΣH2S, as expected for transition metals, whereas Cd, Pb and Zn show an increase (mobilisation). The results suggest that removal of trace elements from anoxic porewaters occurs by coprecipitation (As and Mn) with FeS(s) and/or adsorption (As and Mn) on FeS(s), and by formation of discrete solid sulfides (Cd, Cu, Ni, Pb, Zn and Co). Reactive Fe is extensively sulfidized (51–65%) in both lakes, mostly as pyrite, but also as AVS. Similarities between As, Co, Cu and Ni to Fe ratios in pyrite and their corresponding mean diffusive flux ratios suggest that pyrite is an important sink at depth for these trace elements. High molar ratios of trace elements to Fe in pyrite from Clearwater Lake correspond chronologically to the onset of smelting activities. AVS can be an important reservoir of reactive As, Cd and Ni and, to a lesser extent, of Co, Cu and Pb. Overall, the trace elements most extensively sulfidized were Ni, Cd and As (maximum of 100%, 81% and 49% of the reactive fraction, respectively), whereas Co, Cu, Mn, Pb and Zn were only moderately sulfidized (11–16%). 相似文献
16.
Abdur Rashid Muhammad Ayub Asif Javed Sardar Khan Xubo Gao Chengcheng Li Zahid Ullah Tariq Sardar Juma Muhammad Shahla Nazneen 《地学前缘(英文版)》2021,12(3):101128
This study investigates the values of pH, total dissolved solids (TDS), elevation, oxidative reduction potential (ORP), temperature, and depth, while the concentrations of Br, and potentially harmful metals (PHMs) such as Cr, Ni, Cd, Mn, Cu, Pb, Co, Zn, and Fe in the groundwater samples. Moreover, geographic information system (GIS), XLSTAT, and IBM SPSS Statistics 20 software were used for spatial distribution modeling, principal component analysis (PCA), cluster analysis (CA), and Quantile-Quantile (Q-Q) plotting to determine groundwater pollution sources, similarity index, and normal distribution reference line for the selected parameters. The mean values of pH, TDS, elevation, ORP, temperature, depth, and Br were 7.2, 322 mg/L, 364 m, 188 mV, 29.6 °C, 70 m, 0.20 mg/L, and PHMs like Cr, Ni, Cd, Mn, Cu, Pb, Co, Zn, and Fe were 0.38, 0.26, 0.08, 0.27, 0.36, 0.22, 0.04, 0.43 and 0.86 mg/L, respectively. PHMs including Cr (89%), Cd (43%), Mn (23%), Pb (79%), Co (20%), and Fe (91%) exceeded the guideline values set by the world health organization (WHO). The significant R2 values of PCA for selected parameters were also determined (0.62, 0.67, 0.78, 0.73, 0.60, 0.87, ?0.50, 0.69, 0.70, 0.74, ?0.50, 0.70, 0.67, 0.79, 0.59, and ?0.55, respectively). PCA revealed three geochemical processes such as geogenic, anthropogenic, and reducing conditions. The mineral phases of Cd(OH)2, Fe(OH)3, FeOOH, Mn3O4, Fe2O3, MnOOH, Pb(OH)2, Mn(OH)2, MnO2, and Zn(OH)2 (?3.7, 3.75, 9.7, ?5.8, 8.9, ?3.6, 2.2, ?4.6, ?7.7, ?0.9, and 0.003, respectively) showed super-saturation and under-saturation conditions. Health risk assessment (HRA) values for PHMs were also calculated and the values of hazard quotient (HQ), and hazard indices (HI) for the entire study area were increased in the following order: Cd>Ni>Cu>Pb>Mn>Zn>Cr. Relatively higher HQ and HI values of Ni, Cd, Pb, and Cu were greater than one showing unsuitability of groundwater for domestic, agriculture, and drinking purposes. The long-term ingestion of groundwater could also cause severe health concerns such as kidney, brain dysfunction, liver, stomach problems, and even cancer. 相似文献
17.
Melchor González-Davila 《Geochimica et cosmochimica acta》2005,69(1):83-93
The oxidation of Fe(II) with H2O2 at nanomolar levels in seawater have been studied using an UV-Vis spectrophotometric system equipped with a long liquid waveguide capillary flow cell. The effect of pH (6.5 to 8.2), H2O2 (7.2 × 10−8 M to 5.2 × 10−7 M), HCO3− (2.05 mM to 4.05 mM) and Fe(II) (5 nM to 500 nM) as a function of temperature (3 to 35 °C) on the oxidation of Fe(II) are presented. The oxidation rate is linearly related to the pH with a slope of 0.89 ± 0.01 independent of the concentration of HCO3−. A kinetic model for the reaction has been developed to consider the interactions of Fe(II) with the major ions in seawater. The model has been used to examine the effect of pH, concentrations of Fe(II), H2O2 and HCO3− as a function of temperature. FeOH+ is the most important contributing species to the overall rate of oxidation from pH 6 to pH 8. At a pH higher than 8, the Fe(OH)2 and Fe(CO3)22− species contribute over 20% to the rates. Model results show that when the concentration of O2 is two orders of magnitude higher than the concentration of H2O2, the oxidation with O2 also needs to be considered. The rate constants for the five most kinetically active species (Fe2+, FeOH+, Fe(OH)2, FeCO3, Fe(CO3)22−) in seawater as a function of temperature have been determined. The kinetic model is also valid in pure water with different concentrations of HCO3− and the conditions found in fresh waters. 相似文献
18.
George W. LutherIII Aubin Thibault de Chanvalon Véronique E. Oldham Emily R. Estes Bradley M. Tebo Andrew S. Madison 《Aquatic Geochemistry》2018,24(4):257-277
Manganese oxides, typically similar to δ-MnO2, form in the aquatic environment at near neutral pH via bacterially promoted oxidation of Mn(II) species by O2, as the reaction of [Mn(H2O)6]2+ with O2 alone is not thermodynamically favorable below pH of ~?9. As manganese oxide species are reduced by the triphenylmethane compound leucoberbelein blue (LBB) to form the colored oxidized form of LBB (λmax?=?623 nm), their concentration in the aquatic environment can be determined in aqueous environmental samples (e.g., across the oxic–anoxic interface of the Chesapeake Bay, the hemipelagic St. Lawrence Estuary and the Broadkill River estuary surrounded by salt marsh wetlands), and their reaction progress can be followed in kinetic studies. The LBB reaction with oxidized Mn solids can occur via a hydrogen atom transfer (HAT) reaction, which is a one-electron transfer process, but is unfavorable with oxidized Fe solids. HAT thermodynamics are also favorable for nitrite with LBB and MnO2 with ammonia (NH3). Reactions are unfavorable for NH4+ and sulfide with oxidized Fe and Mn solids, and NH3 with oxidized Fe solids. In laboratory studies and aquatic environments, the reduction of manganese oxides leads to the formation of Mn(III)-ligand complexes [Mn(III)L] at significant concentrations even when two-electron reductants react with MnO2. Key reductants are hydrogen sulfide, Fe(II) and organic ligands, including the siderophore desferioxamine-B. We present laboratory data on the reaction of colloidal MnO2 solutions (λmax?~?370 nm) with these reductants. In marine waters, colloidal forms of Mn oxides (<?0.2 µm) have not been detected as Mn oxides are quantitatively trapped on 0.2-µm filters. Thus, the reactivity of Mn oxides with reductants depends on surface reactions and possible surface defects. In the case of MnO2, Mn(IV) is an inert cation in octahedral coordination; thus, an inner-sphere process is likely for electrons to go into the empty e g * conduction band of its orbitals. Using frontier molecular orbital theory and band theory, we discuss aspects of these surface reactions and possible surface defects that may promote MnO2 reduction using laboratory and field data for the reaction of MnO2 with hydrogen sulfide and other reductants. 相似文献
19.
Atomic emission spectrographic analysis of the trace inorganic constituents of marine humic substances gave the following range of concentrations: Si, 200 ppm to > 2%; Al, 400 ppm to ~ 1%; Fe, 600–3000 ppm; Ca, 600 ppm to > 2%; Mg, 20–6000 ppm; Na, 600 ppm to > 2%; Ag, < 6–600 ppm; B, < 60–1000 ppm; Cu, 600–4000 ppm; Mn, 8–100 ppm; Mo, <20–3000 ppm; Ni, 100–1000 ppm; Pb, < 40–600 ppm; Sn, 40–600 ppm; Ti, < 20–2500 ppm; V, 20–200 ppm; Zn, 350–4500 ppm; Zr, < 60–500 ppm.Humic substances contain a sizeable portion of the Cu, Mo and Zn found in sediments, but are less important for Ni, Co and Pb, and are insignificant for the Mn, V and Fe content. The metals are mostly introduced into the humates during their diagenetic formation in sediment by dissolution of metals from various mineralogical phases. A precursor of the sedimentary humates, the polymeric organic material dissolved in interstitial water, contains most of the Cu and Zn, about half of the Ni, Fe and Co, and very little of the Mn found in interstitial water. Comparison of the data on humates with that obtained by H2O2 treatment of sediments indicates that Cu, Zn and possibly most of the Mo are associated with organic matter, but that Ni and Co are associated with sulfides. 相似文献
20.
A radioisotope energy-dispersive X-ray (EDX) system has been used on board the German research vessel “Valdivia” during an exploration expedition in the northern equatorial Pacific in 1973. The instrumentation used consisted of an X-ray detection system incorporating a 30 mm2 effective-area Si (Li) detector with a measured energy resolution of 195 eV for Mn Kα X-rays, standard nuclear electronics, a 1024-channel analyser and a data read-out unit. The X-ray spectra in the manganese-nodule samples were excited by a 30-mCi 238Pu source.The six elements Mn, Fe, Co, Ni, Cu and Zn were analysed on board. Precision values for the analyses were less than 3% for Mn, Fe, Ni, Cu and Zn and about 5% for Co. A total amount of 350 analyses was carried out during a one-month cruise.Average contents of 190 analysed whole manganese-nodule samples from all the sampling sites of the covered area were 23.3% Mn, 6.7% Fe, 0.23% Co, 1.16% Ni, 0.94% Cu and 0.10% Zn. The average content of the base metals expressed as the sum of the Co, Ni, Cu and Zn contents was 2.48%. A linear relationship between Mn and Ni in all analysed samples, including whole manganese-nodule samples, zones of manganese nodules and manganese crusts, was observed. The Mn/Ni ratio calculated by regression analysis was 23.0. Zonal variations of the chemical contents of the six elements in the manganese nodules were found. A size classification of the manganese nodules has been suggested. Geochemical correlations of Cu and Ni versus Mn/Fe in the investigated samples are given. 相似文献