Processes controlling the heavy metal distribution in pacific ferromanganese nodules and crusts

The ferromanganese precipitates existing in deep-sea waters of the Pacific consist of two types of deposits: (1) nodules mainly are distributed in pelagic basins beneath the CCD (Calcite Compensation Depth) where the rate of sedimentation is low; (2) polymetallic encrustations are formed on exposed seamount rocks where currents prevent normal sediment accumulation. Nodules, being formed in areas bordering the equatorial zone of high biological productivity, grow by two different processes: (A) early diagenetic growth by supply of metals and metal compounds from pore water and (B) hydrogenetic growth by supply of colloidal particles from near-bottom seawater. These processes lead to different kinds of oxide and different metal contents. The diagenetic growth process takes place under oxidizing to suboxidizing conditions and is supplied by an ionic solution of Mn²⁺ and other divalent metal ions. The mobilization of Mn is caused by the decomposition of organic matter. The growth features of the early diagenetic nodules show alternating laminae of crystalline and amorphous material. These rhythmic sequences of different microlayers are explained by physico-chemical changes (variation of pH) in the microenvironment of the accreting nodule surface. The hydrogenetic crust growth on seamounts leads to ferromanganese precipitates which are in particular rich in Co. The Co concentration is inversely related to the water depth. Co is positively correlated to Mn which can be derived from the oxygen minimum zone. Contrary to the diagenetic nodule growth, the crust accretion is also a colloidal precipitation process. In the water column below the oxygen minimum zone, a mixture of particles of Mn-Fe-oxyhydroxide and silicate accrete together on the surface of substratum rocks. Surface chemical mechanisms control the enrichment of Ni, Co, Pb, and other metals from the seawater; for Pt, a coprecipitation with MnO₂ caused by a redox reaction is proposed. Distinct oceanographical and geological conditions enable or promote, respectively, the ferromanganese crust formation on seamounts.     

A comparison of the lead phosphates from the Oxidised Zone,broken hill ore body,with those of some other Australian localities

A method of using the X‐ray fluorescence spectrometer has been adopted for the analyses of lead phosphates, and eight samples of phosphates from Broken Hill and three from the Flinders Ranges, South Australia, were analysed by this means. Of these, five were found to be mimetite and six pyromorphite, several being rich in calcium. Dividing the sources into geochemical areas we find that the specimens from Broken Hill have no vanadium and a low alkaline metal earth content while those from the Flinders Ranges have a small, but noticeable vanadium content and high alkaline metal earth content. A poorer X‐ray diffraction fit of a calcium‐rich mimetite to the hexagonal structure indicates that the monoclinic structure could be of more importance in the members of this composition.     

Effects of Coal Rank and High Organic Sulfur on the Structure and Optical Properties of Coal-based Graphene Quantum Dots

Coal‐based graphene quantum dots (GQDs) were successfully produced via a one‐step chemical synthesis from six different coal ranks, from which two superhigh organic sulfur (SHOS) coals were selected as natural S‐doped carbon sources for the preparation of S‐doped GQDs. The effects of coal properties on coal‐based GQDs were analyzed by means of high‐resolution transmission electron microscopy (HRTEM), X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, X‐ray photoelectron spectroscopy (XPS), ultraviolet‐visible (UV‐Vis) absorption spectroscopy, and fluorescence emission spectra. It was shown that all coal samples can be used to prepare GQDs, which emit blue‐green and blue fluorescence under ultraviolet light. Anthracite‐based GQDs have a hexagonal crystal structure without defects, the largest size, and densely arranged carbon rings in their lamellae; the high‐rank bituminous coal‐based GQDs are relatively reduced in size, with their hexagonal crystal structure being only faintly visible; the low‐rank bituminous coal‐based GQDs are the smallest, with sparse lattice fringes and visible internal defects. As the metamorphism of raw coals increases, the yield decreases and the fluorescence quantum yield (QY) initially increases and then decreases. Additionally, the surface of GQDs that were prepared using high‐rank SHOS coal (high‐rank bituminous coal) preserves rich sulfur content even after strong oxidation, which effectively adjusts the bandgap and improves the fluorescence QY. Thus, high‐rank bituminous coal with SHOS content can be used as a natural S‐doped carbon source to prepare S‐doped GQDs, extending the clean utilization of low‐grade coal.     

Comparison in Mineralization between Ferromanganese Nodules and Co-Rich Manganese Crusts in Pacific Ocean

The ferromanganese deposits in the deep- sea floor of thePacific Ocean are classified as two types:polymetallic nodule(hereafter shortened as nodule) and Co- rich crust(hereaftershortened as crust) . The comparative research between thenodule and the crust shows that several similarities and differ-ences are present geochemically between them.Both the nod-ule and the crust consisting of manganese and iron oxide andhydroxide that contain some of transitional and divalent metalelements such as …     

Non‐Destructive or Noninvasive? The Potential Effect of X‐Ray Fluorescence Spectrometers on Luminescence Age Estimates of Archaeological Samples

The non‐destructive nature of X‐ray fluorescence (XRF) spectrometers is a principal reason for an increase in their use in archaeological science over the last 15 years, especially for analyzing museum‐curated artifacts and in situ site fabrics. Here, we show that low‐power XRF spectrometry can be detrimental for luminescence dating (surface applications such as mud‐wasp nest dating in particular). We investigated the effects of irradiation by X‐rays emitted from handheld and benchtop spectrometers on optically stimulated luminescence (OSL) signals. Measurements were taken using a portable OSL (pOSL) unit on the following unprepared archaeological materials: sedimentary quartz grains, pottery, a mud‐wasp nest, stone tools, and a rock flake with anthropogenically applied pigment and natural pigmentation (iron oxides). We observed an increase in luminescence compared to initial background counts for all materials tested, which could lead to overestimation of age determinations in some situations. Our experiment provides a reminder of the potential effects of X‐ray radiation, and the need for thorough documentation of all recording and analytical techniques applied to archaeological materials.     

Phase associations and potential selective extraction methods for selected high-tech metals from ferromanganese nodules and crusts with siderophores

Deep-sea ferromanganese deposits contain a wide range of economically important metals. Ferromanganese crusts and nodules represent an important future resource, since they not only contain base metals such as Mn, Ni, Co, Cu and Zn, but are also enriched in critical or rare high-technology elements such as Li, Mo, Nb, W, the rare earth elements and yttrium (REY). These metals could be extracted from nodules and crusts as a by-product to the base metal production. However, there are no proper separation techniques available that selectively extract certain metals out of the carrier phases. By sequential leaching, we demonstrated that, except for Li, which is present in an easily soluble form, all other high-tech metals enriched in ferromanganese nodules and crusts are largely associated with the Fe-oxyhydroxide phases and only to subordinate extents with Mn-oxide phases. Based on this fact, we conducted selective leaching experiments with the Fe-specific organic ligand desferrioxamine-B, a naturally occurring and ubiquitous siderophore. We showed by leaching of ferromanganese nodules and crusts with desferrioxamine-B that a significant and selective extraction of high-tech metals such as Li, Mo, Zr, Hf and Ta is possible, while other elements like Fe and the base metals Mn, Ni, Cu, Co and Zn are not extracted to large extents. The set of selectively extracted elements can be extended to Nb and W if Mn and carbonate phases are stripped from the bulk nodule or crust prior to the siderophore leach by e.g. a sequential leaching technique. This combination of sequential leaches with a siderophore leach enhanced the extraction to 30–50% of each Mo, Nb, W and Ta from a mixed type Clarion-Clipperton Zone (CCZ) nodule and 40–80% from a diagenetic Peru Basin nodule, whilst only 5–10% Fe and even less Mn are extracted from the nodules. Li is extracted to about 60% from the CCZ nodule and a maximum of 80% Li is extracted from the Peru Basin nodule.Our pilot work on selective extraction of high-tech metals from marine ferromanganese nodules and crusts showed that specific metal-binding organic ligands may have promising potential in future processing technologies of these oxide deposits.     

Assessment of acoustic backscatter intensity surveying on deep-sea ferromanganese crust: Constraints from Weijia Guyot,western Pacific Ocean

Near-bottom observation data from the manned deep submersible Jiaolong with high-precision underwater positioning data from Weijia Guyot, Magellan Seamounts in the Western Pacific Ocean are reported. Three substrate types were identified: Sediment, ferromanganese crust, and ferromanganese crust with a thin cover of sediment. The ferromanganese crusts show clear zoning and their continuity is usually disturbed by sediments on areas of the mountainside with relatively gentle slope gradients. The identified substrate spatial distributions correspond to acoustic backscatter intensity data, with regions of high intensity always including crust development and regions of low intensity always having sediment. Therefore, acoustic backscatter intensity surveying appears useful in the delineation and evaluation of crust resources, although further more work is needed to develop a practicable methodology.     

Role of organic matter in the accumulation of platinum in oceanic ferromanganese deposits

In order to elucidate possible processes leading to platinum accumulation in ferromanganese deposits, we analyzed published data on the interaction of dissolved platinum species in different valence states with iron and manganese oxyhydroxides under oceanic conditions and experimentally studied the kinetics of sorption of inorganic and organic complexes of platinum (II) and platinum (IV) on synthetic iron and manganese oxyhydroxides and natural materials (marine colloids, and ferromanganese crust samples). The role of dissolved and suspended particulate aquatic organic matter in the sorption accumulation of platinum was evaluated. Possible reasons for the preferential (compared with other noble metals) accumulation of platinum in oceanic ferromanganese deposits were discussed.     

Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.     

Quantitative micro‐X‐ray fluorescence scanning spectroscopy of wet sediment based on the X‐ray absorption and emission theories: Its application to freshwater lake sedimentary sequences

Micro‐X‐ray fluorescence scanning spectroscopy of marine and lake sedimentary sequences can provide detailed palaeoenvironmental records through element intensity proxy data. However, problems with the effects of interstitial pore water on the micro‐X‐ray fluorescence intensities have been pointed out. This is because the X‐ray fluorescence intensities are measured directly at the surfaces of split wet sediment core samples. This study developed a new method for correcting X‐ray fluorescence data to compensate for the effects of pore water using a scanning X‐ray analytical microscope. This involved simultaneous use of micro‐X‐ray fluorescence scanning spectroscopy and an X‐ray transmission detector. To evaluate the interstitial pore water content from the X‐ray transmission intensities, a fine‐grained sediment core retrieved from Lake Baikal (VER99‐G12) was used to prepare resin‐embedded samples with smooth surfaces and uniform thickness. Simple linear regression between the linear absorption coefficients of the samples and their porosity, based on the Lambert–Beer law, enabled calculation of the interstitial pore spaces and their resin content with high reproducibility. The X‐ray fluorescence intensities of resin‐embedded samples were reduced compared with those of dry sediment samples because of: (i) the X‐ray fluorescence absorption of resin within sediment; and (ii) the sediment dilution effects by resin. An improved micro‐X‐ray fluorescence correction equation based on X‐ray fluorescence emission theory considers the instrument's sensitivity to each element, which provides a reasonable explanation of these two effects. The resin‐corrected X‐ray fluorescence intensity was then successfully converted to elemental concentrations using simple linear regression between the data from micro‐X‐ray fluorescence scanning spectroscopy and from the conventional analyzer. In particular, the calculated concentration of SiO₂ over the depth of the core, reflecting diatom/biogenic silica concentration, was significantly changed by the calibrations, from a progressively decreasing trend to an increasing trend towards the top of the core.     

Removal of Lead,Copper, Zinc and Cadmium from Water Using Phosphate Rock

Removal of Pb^2＋, Cu^2＋, Zn^2＋ and Cd^2＋ from aqueous solutions by sorption on a natural phosphate rock （FAP） was investigated. The effects of the contact time and initial metal concentration were examined in the batch method. The percentage sorption of heavy metals from solution ranges generally between 50% and 99%. The amount of sorbed metal ions follows the order Cu〉Pb〉Cd〉Zn. Heavy metal immobilization was attributed to both surface complexation of metal ions on the surface of FAP grains and partial dissolution and precipitation of a heavy metal-containing phosphate. The very low desorption ratio of heavy metals further supports the effectiveness of FAP as an alternative and low-cost material to remove toxic Pb^2＋, Cu^2＋, Zn^2＋ and Cd^2＋ from polluted waters.     

Is X‐ray core scanning non‐destructive? Assessing the implications for optically stimulated luminescence (OSL) dating of sediments

Optically stimulated luminescence (OSL) dating is widely used to date clastic deposits, including those collected by coring. X‐ray scanning of cores has become popular because of the rapidly acquired, high‐resolution information it gives about optical, radiographic and elemental variations. Additionally, X‐ray scanning is widely viewed as a non‐destructive method. However, such instruments use an intense X‐ray beam that irradiates the split core to enable both X‐radiographic and X‐ray fluorescence (XRF) analysis. This irradiation will influence the optically stimulated luminescence signal in the sediments. This study determines the radiation dose delivered to sediments in a core during an X‐ray scan, and assesses the implications for studies wishing to combine X‐ray scanning and OSL dating. Copyright © 2009 John Wiley & Sons, Ltd.     

广西岩溶区土壤铁锰结核重金属富集的地质特征

广西岩溶区农田土壤重金属污染形势严峻。该地区土壤含有大量铁锰结核,其主要成分为铁和锰的氧化物,对重金属有着较强的富集作用。铁锰结核伴随着土壤形成过程而产生,也是反映土壤形成过程及成土环境变化的良好载体。研究铁锰结核中重金属的富集特征有助于了解广西岩溶区土壤中重金属元素的富集过程和富集特征。文章对广西柳江和桂平的土壤与其中的铁锰结核进行了成分分析,通过微量元素分析得到铁锰结核对Ni、Cu、Cd、Zn、Pb、Co、Ba、As、Cr等重金属元素的富集特征,通过Ti/Al2O3的比值关系推断了铁锰结核与土壤的物质来源。此外,还对铁锰结核进行了激光共聚焦显微拉曼光谱仪（Laser Microscopic Confocal Raman Spectrometer）、扫描电镜和能谱仪（SEM-EDS）分析。通过铁锰结核内部同心环带状圈层结构及其内部的元素分布周期性变化的特征,推测结核形成机制。铁锰结核的形成固定了大量重金属元素,减轻了土壤重金属污染负担;但如果铁锰结核发生了溶解则会导致Mn及受其控制的部分重金属（Co、Cu、Ni、Ba）重新释放回到土壤,加重重金属污染。     

Geochemical Features and Tectonic Setting of Greenstones from Kunimiyama, Northern Chichibu Belt, Central Shikoku, Japan

Abstract. We report whole‐rock chemical data for the greenstones from the Kunimiyama area in the Northern Chichibu Belt and their implications on the tectonic setting of these rocks. The Kunimiyama greenstones are associated with stratiform fer‐romanganese deposits or bedded cherts in the northern part of the study area, but are closely associated with a thick limestone block or bedded cherts in the southern part. The constituent minerals of greenstones are albitized plagioclase, clinopy‐roxene, chlorite, calcite, epidote, pumpellyite, prehnite, quartz, celadonite, sericite and opaque minerals such as iron oxyhy‐droxide and hematite. These mineral assemblages, epidote + pumpellyite + chlorite and chlorite + pumpellyite + prehnite, suggest that the metamorphic grade of greenstones from the Kunimiyama area is prehnite‐pumpellyite facies. The whole‐rock chemical compositions of greenstones associated with ferromanganese deposits are generally similar to those of normal mid‐ocean ridge basalt (N‐MORB). In contrast, the chemical compositions of the greenstones associated with the limestone block are comparable to those of ocean island alkaline basalt. Greenstones associated with bedded cherts are of enriched MORB and ocean island basalt, as well as N‐MORB origins, suggesting they probably formed as a result of plume‐related MOR volcanism in the Panthalassa Ocean in Early Permian and by tectonic mixing of ocean island basalts with oceanic ridge crustal fragments during accretion/subduction processes. These geological and geochemical lines of evidence suggest that the Kunimiyama greenstones are allochthonous blocks of accreted oceanic crust and seamounts. The ferromanganese deposits are frequently accompanied by reddish greenstones. Compared to common greenish greenstones, the reddish greenstones are characterized by high MnO and rare earth element contents and distinct negative Ce anomalies, implying a slight contribution of hydro thermal component forming the ferromanganese deposits.     

Incorporation of U,Pb and Rare Earth Elements in Calcite through Crystallisation from Amorphous Calcium Carbonate: Simple Preparation of Reference Materials for Microanalysis

Uncertainty for elemental and isotopic measurements in calcite by LA‐ICP‐MS is largely controlled by the homogeneity of the reference materials (RMs) used for calibration and validation. In order to produce calcite RMs with homogeneous elemental and isotopic compositions, we incorporated elements including U, Pb and rare earth elements into calcite through heat‐ and pressure‐induced crystallisation from amorphous calcium carbonate that was precipitated from element‐doped reagent solution. X‐ray absorption spectra showed that U was present as U(VI) in the synthesised calcite, probably with a different local structure from that of aqueous uranyl ions. The uptake rate of U by our calcite was higher in comparison with synthetic calcite of previous studies. Variations of element mass fractions in the calcite were better than 12% 2RSD, mostly within 7%. The ²⁰⁷Pb/²⁰⁶Pb ratio in the calcite showed < 1% variations, while the ²³⁸U/²⁰⁶Pb ratio showed 3–24% variations depending on element mass fractions. Using the synthetic calcite as primary RMs, we could date a natural calcite RM, WC‐1, with analytical uncertainty as low as < 3%. The method presented can be useful to produce calcite with controlled and homogeneous element mass fractions and is a promising alternative to natural calcite RMs for U‐Pb geochronology.     

Electron Probe Microanalysis of Bromine in Minerals and Glasses with Correction for Spectral Interference from Aluminium,and Comparison with Microbeam Synchrotron X‐Ray Fluorescence Spectrometry

The strong spectral interference between Br‐ and Al‐induced X‐ray lines hampers the utilisation of electron probe microanalysis (EPMA) for measuring Br mass fractions in Al‐bearing minerals and glasses. Through measuring Br‐free Al‐bearing materials, we established an EPMA method to quantify the overlap from AlKα on BrLβ, which can be expressed as a linear function of the Al₂O₃ content. The count rate of the BrLβ peak signal was enhanced by high beam currents and long measurement times. Application of this EPMA method to Al‐ and Br‐bearing materials, such as sodalite and scapolite, and to five experimental glasses yielded Br mass fractions (in the range of 250–4000 μg g^?1) that are consistent with those measured by microbeam synchrotron X‐ray fluorescence (μ‐SXRF) spectrometry. The EPMA method has an estimated detection limit of ~ 100–300 μg g^?1. We propose that this method is useful for measuring Br mass fractions (hundreds to thousands of μg g^?1) in Al‐bearing minerals and glasses, including those produced in Br‐doped experiments. In addition, the natural marialitic scapolite (ON70) from Mpwapwa (Tanzania) containing homogeneously distributed high mass fractions of Br (2058 ± 56 μg g^?1) and Cl (1.98 ± 0.03% m/m) is an ideal reference material for future in situ analyses.     

Depositional Age of a Fossil Whale Bone from São Paulo Ridge,South Atlantic Ocean,Based on Os Isotope Stratigraphy of a Ferromanganese Crust

Whale carcasses (whale falls) deposited on the deep seafloor are associated with a distinctive biotic community. A fossil whale bone recovered from São Paulo Ridge, South Atlantic Ocean, during cruise YK13–04 Leg 1 of R/V Yokosuka was covered by a ferromanganese (Fe–Mn) crust approximately 9 mm thick. Here, we report an age constraint for this fossil bone on the basis of Os isotopic stratigraphy (¹⁸⁷Os/¹⁸⁸Os ratio) of the Fe–Mn crust. Major‐ and trace‐element compositions of the crust are similar to those of Fe–Mn crusts of predominantly hydrogenous origin. Rare earth element concentrations in samples of the crust, normalized with respect to Post‐Archean average Australian Shale, exhibit flat patterns with positive Ce and negative Y anomalies. These results indicate that the Fe–Mn crust consists predominantly of hydrogenous components and that it preserves the Os isotope composition of seawater at the time of its deposition. ¹⁸⁷Os/¹⁸⁸Os ratios of three Fe–Mn crust samples increased from 0.904 to 1.068 in ascending stratigraphic order. The value of 1.068 from the surface slice (0–3 mm depth in the crust) was identical to that of present‐day seawater within error (~1.06). The value of 0.904 from the basal slice (6–9 mm) equaled seawater values from ca. 4–5 Ma. Because it is unknown how long the bone lay on the seafloor before the Fe–Mn crust was deposited, the Os stratigraphic age of ca. 5 Ma is a minimum age of the fossil. This is the first application, to our knowledge, of marine Os isotope stratigraphy for determining the age of a fossil whale bone. Such data may offer valuable insights into the evolution of the whale‐fall biotic community.     

Determination of Platinum‐Group Elements and Gold in Ferromanganese Nodule Reference Samples

A measurement procedure for determining of Ru, Pd, Ir, Pt and Au mass fractions in ferromanganese deposits by inductively coupled plasma‐mass spectrometry after acid digestion and anion exchange preconcentration is presented. To eliminate incomplete recovery after sorption preconcentration of the platinum‐group elements (PGE) and Au, a standard addition method was used. Detection limits ranged from 0.02 ng (Pd, Ir) to 0.19 ng (Ru). The measurement results for ferromanganese nodule reference material NOD‐A‐1 and NOD‐P‐1 agree with earlier reported values. Intermediate precision of PGE concentration data for nodule reference materials in this work was 5–24% (1s) and could reflect sample heterogeneity.     

厚结壳的形成条件及控制因素分析

当前对于大洋厚结壳的研究较少,而厚结壳是未来开发利用的重点,同时它记录的地质历史长,控制和影响结壳生长发育的各种因素必然能在厚结壳上充分体现出来。因此,开展厚结壳的形成条件及控制因素的研究,具有重要的理论与现实意义。文章利用GIS空间分析技术与地质统计方法,对厚结壳的定义、结壳厚度与水深、结壳厚度与基岩、结壳生长与构造活动、结壳厚度与沉积速率、结壳厚度与经纬度、结壳厚度与主成矿元素之间的关系进行了分析,结果表明,结壳的厚度变化受控于水深、基岩、构造活动、沉积速率、经纬度等因素,同时结壳厚度与主成矿元素之间存在明显的相关性。     

Copper Speciation in a Collection of Geochemical Reference Materials Using Sequential Extraction and Evaluation of the Validity Using XANES Spectroscopy

Copper speciation in a collection of Japanese geochemical reference materials (JSO‐1, JLk‐1, JSd‐1, ‐2, ‐3 and ‐4, JMs‐1 and JMs‐2) was achieved by sequential extraction and characterised using X‐ray absorption near‐edge structure spectroscopy. In the first step of the extraction, referred to as the acid fraction, between 1% and 20% total Cu within the reference materials was extracted. Such a result is typically accounted for by absorption of Cu onto clay minerals. However, the presence of Cu sulfate (an oxidation product of chalcopyrite) was observed in some of the stream sediments affected by mining activity (JSd‐2 and JSd‐3) instead. Copper was extracted in the reducible fraction (targeting Fe hydroxide and Mn oxide) (2–49% total Cu). Between 2% and 51% Cu was extracted in the oxidised fraction (targeting sulfides and organic matter). X‐ray absorption near‐edge structure spectroscopy clarified that the reducible fraction consisted of Cu bound to Fe hydroxide, whereas the oxidised fraction was a mixture of Cu bound to humic acid (HA) and Cu sulfide. In the oxidisable fraction, chalcopyrite was the predominant species identified in JSd‐2, and Cu bound to HA was the major species identified in JSO‐1 (a soil sample).