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1.
Trichloroethene (TCE) is one of the most common pollutants in groundwater, and Cs+ can be a cocontaminant at nuclear facilities. Smectite clays have large surface areas, are common in soils, have high affinities for some organic contaminants, and hence can potentially influence the transport of organic pollutants entering soils and sediments. The exchangeable cations present near smectite clay surfaces can radically influence the sorption of organic pollutants by soil clays. This research was undertaken to determine the effect of Cs+, and other common interlayer cations, such as K+ and Ca2+, on the sorption of TCE by a reference smectite clay saponite. Cs-saturated clay sorbed the most TCE, up to 3500 mg/kg, while Ca-saturated smectite sorbed the least. We hypothesize that the stronger sorption of TCE by the Cs-smectite can be attributed to the lower hydration energy and hence smaller hydrated radius of Cs+, which expands the lateral clay surface domains available for sorption. Also, Cs-smectite interlayers are only one or two water layers thick, which may drive capillary condensation of TCE. Our results implicate enhanced retention of TCE in aquifer materials containing smectites accompanied by Cs+ cocontamination.  相似文献   

2.
Sorption of two dinitrophenolic herbicides, 4,6-dinitro-o-cresol (DNOC) and 4,6-dinitro-2-sec-butylphenol (DINOSEB) to smectite was studied using FTIR, HPLC, and quantum chemical methods. The high affinity of DNOC and DINOSEB for smectite surfaces was attributed to site-specific interactions with exchangeable cations and nonspecific van der Waals interactions with the siloxane surface. The positions of the nu(asym)(NO) and nu(sym)(NO) vibrational modes were perturbed by the exchangeable cations with similar changes occurring for both alkali and alkaline earth cations as a function of ionic potential. The cation-induced changes to the vibrational bands of the NO2 groups indicate that exchangeable metal cations are coordinated to -NO2 groups. Quantum chemical methods predicted a red-shift of the nu(asym)(NO) band and a corresponding blue-shift of the nu(sym)(NO) modes, as was observed experimentally. The nature of the smectite surface itself did not strongly influence the vibrational modes of sorbed DNOC or DINOSEB on the basis of a comparison of DNOC sorbed to three different smectites (K-SWy-2, K-SAz-1, and K-SHCa-1). FTIR spectra of DNOC and DINOSEB sorbed to a K-SWy-2 smectite were studied quantitatively using a modified form of Beers law. The FTIR-derived sorption isotherm of DNOC sorbed to K-SWy-2 was in good agreement with the isotherm derived from HPLC measurements. The molar absorptivity value of DNOC sorbed to K-SWy-2 smectite was 1.43 x 10(7) cm2/mol in good agreement with literature values for nitroaromatics (average value of 1.72 x 10(7) +/- 0.3 cm2/mol). On the basis of this value, the limit of detection using the FTIR method of approximately 5 microgDNOC g(clay) was determined. These two observations (sorption isotherms and molar absorptivity) provide a direct link between the macroscopic sorption results and the FTIR spectra.  相似文献   

3.
The objective of this work was to test two possible sorption mechanisms of organic chemicals to montmorillonite: n-π electron-donor-acceptor (EDA) interaction with lone electron pairs of siloxane oxygens (n-donors) and complexation with exchangeable cations. Batch sorption experiments were performed for 1,3-dinitrobenzene, 1,4-dinitrobenzene (π-electron acceptors and cation binders), and hexafluorobenzene (π-electron acceptor only) to homoionic montmorillonites in water or hexane. For all three sorbates, the aqueous sorption affinity showed large cation dependency (Cs(+) > K(+) > Na(+)), wherein sorption of hexafluorobenzene to Cs(+)-montmorillonite was the strongest (K(d) in the order of 10(4) L/kg). Change of the solvent media from water to hexane generally favored sorption, indicating suppressive effect by cation hydration. Cosorption of 1,4-dinitrobenzene prominently decreased sorption of 1,3-dinitrobenzene to all cation-exchanged montmorillonites; however, hexafluorobenzene caused strong competition only to Cs(+)-montmorillonite. Furthermore, complexation of exchangeable cations by 18-crown-6 ether dramatically suppressed sorption of 1,3-dinitrobenzene to K(+)-montmorillonite in water and all cation-exchanged montmorillonites in hexane, but not to the rest. The contrast patterns of binary competitive sorption between nitroaromatics and hexafluorobenzene indicated they sorbed to different sites on montmorillonite. It was proposed that sorption of hexafluorobenzene was dominated by n-π EDA interaction, while sorption of nitroaromatics was dominated by cation-polar interaction.  相似文献   

4.
Pesticide adsorption by soil clays can be dramatically influenced by the exchangeable cations present. Among the common exchangeable base cations in soils (Ca2+, Mg2+, K+, and Na+), K+-saturated clays frequently demonstrate the strongest affinity for pesticides. In the presence of multiple exchangeable cations in the system, we hypothesize that the magnitude of pesticide sorption to soil minerals is proportional to the fraction of clay interlayers saturated with K+ ions. To test this hypothesis, we measured sorption of three pesticides with different polarities (dichlobenil, monuron, and biphenyl) by homoionic K- and Ca-smectite (SWy-2) in KCl/CaCl2 aqueous solutions. The presence of different amounts of KCl and CaCl2 resulted in varying populations of K+ and Ca2+ on the clay exchange sites. The sorption of dichlobenil and, to a lesser extent monuron, increased with the fraction of K+ on clay mineral exchange sites. Ca- and K-SWy-2 displayed the same sorption capacities for nonpolar biphenyl. X-ray diffraction patterns indicated that at lower fractions of K+-saturation, exchangeable K+ ions were randomly distributed in clay interlayers and did not enhance pesticide sorption. At higher populations of K+ (vs Ca2+), demixing occurred causing some clay interlayers, regions, or tactoids to become fully saturated by K+, manifesting greatly enhanced pesticide sorption. The forward and reverse cation exchange reactions influenced not only K+ and Ca2+ populations on clays but also the nanostructures of clay quasicrystals in aqueous solution which plays an important, if not dominant, role in controlling the extent of pesticide sorption. Modulating the cation type and composition on clay mineral surfaces through cation exchange processes provides an environmental-safe protocol to manipulate the mobility and availability of polar pesticides, which could have applications for pesticide formulation and in environmental remediation.  相似文献   

5.
Sorption of volatile organic compounds (VOCs) in low organic carbon (<0.1%) geosorbents is difficult to predict because the sorption capacity of the mineral matrix is poorly understood. This research demonstrates hydrophobic micropores can be important sorption sites for VOCs. We studied the sorption of water and TCE on three dealuminated Y zeolites ranging from hydrophilic (CBV-300) to hydrophobic (CBV-720 and CBV-780), with the surface cation density decreasing from 2.07 to 0.42 and 0.16 sites/ nm2, respectively. Water sorption and dehydration data indicate water affinity of the zeolite micropores decreases with micropore hydrophobicity. TCE sorption on the wet zeolites decreased with increasing surface cation density. At a relative pressure (P/P0) of 0.136, TCE filled only 0.034% of the micropore volume in wet CBV-300, but 16.9% and 18.6% in wet CBV-720 and CBV-780, respectively. TCE desorption data from dry and wet silica sand (Min-U-Sil 30), kaolinite (KGa-1), and smectite (SWy-1) confirmed VOC sorption in wet microporous minerals is controlled by both the micropore volume and hydrophobicity. Results suggestTCE adsorbs in hydrophobic micropores by displacing loosely bound water, consistent with the theoretical considerations indicating the process of transferring loosely bound water from hydrophobic micropores to the bulk phase is energetically favorable.  相似文献   

6.
Soil cations were desorbed by electro-ultrafiltration (EUF), i.e. by applying an external electric field to aqueous suspensions, and collecting the cations by ultrafiltration. Three different field strengths were used to obtain several cation fractions in a single extraction run lasting 35 min. Potassium desorbed in 10 min (K10) was closely correlated with the equilibrium activity ratio (AR0) of soil K measured in 0.01M CaCl2, for all but the sandy loam soils, while that desorbed in 35 min (K35) was less than the exchangeable K, but correlated closely with it. EUF values compared favourably with other soil K parameters, determined by conventional methods, for predicting uptake of K by rye-grass from ten soils during intensive cropping in the glasshouse. Sodium desorbed in 35 min (Na35) approximated to the exchangeable Na, although most of it was desorbed in the first 15 min. Na10 and Na35 accounted for about 56% of the variation in Na uptake by ryegrass at the first cut, and 68% of the variation in the cumulative uptake at the sixth cut. Between 9–24% of the exchangeable calcium was desorbed in 35 min, and magnesium desorbed was closely correlated with both the Mg concentration of the soil saturation extract and the exchangeable Mg. EUF extraction of Mg is less satisfactory than for K, Na and Ca owing to the precipitation of Mg(OH)2 on the cathode filter.  相似文献   

7.
The buildup of phosphorus (P) in the soil is a major factor limiting the operating life of a wastewater land treatment system. In this study, we evaluated changes of chemical properties, P profiles, and adsorption isotherms in the soils of a Muskegon wastewater land treatment system, which has received wastewater for approximately 30 years. It was found that the pH in the 15-cm topsoil increased from approximately 5-6 in 1973 to approximately 7.4-7.8 in 2003; a large amount of salt (e.g., Ca, Mg) in wastewater was adsorbed by the soil; the soil Al content (either exchangeable or oxalate extractable) decreased, while the oxalate-extractable Fe content remained at the same level. Ca-bound P accounted for > or = 70% of the total P adsorbed in the soil. The soil P adsorption capacity increased and was positively correlated with the concentration of exchangeable Ca in the soil. A higher concentration of exchangeable Ca was found in the 15-cm topsoil, where a higher total organic carbon was present. More P was accumulated in the upper soil than in the deeper soil. The adsorption of Ca in wastewater by the soil may extend the life expectancy of the Muskegon land treatment system.  相似文献   

8.
为探讨江西紫色土交换性钙、镁含量及对烟叶钙、镁含量分布的影响,于2009年在江西紫色土烟区点对点采集土样和烟样进行了化验分析。结果表明,江西紫色土交换性钙含量丰富但变异较大,交换性镁含量偏低且交换性钙、镁比值较大,导致烟叶含钙量变异较大且烟叶含镁量较低;烟叶含镁量为中性紫色土>酸性紫色土>碱性紫色土;中性紫色土烤烟不同叶位烟叶含钙、镁量差异不大,但碱性与酸性紫色土烤烟均为上部烟叶含钙、镁量高于中下部叶;土壤交换性钙、镁之间呈极显著正相关,交换性钙、镁与土壤pH、有机质和氮、磷、钾、硫之间具有一定的相关性,但交换性钙与微量元素呈极显著负相关。  相似文献   

9.
Tetracycline (TC) and chlortetracycline (CTC) are used extensively for growth promotion and therapeutic purposes in livestock production. The sorption of TC and CTC on clays, humic substances (HS), and clay-humic complexes (clay-HC) derived from two agricultural soils was quantified using dilute CaCl2 (Ca) and KCI (K) as background solutions. In all systems, the soil components sorbed > 96% of added tetracyclines. Strongest sorption was observed for clays, followed by HS, and then clay-HC. Greater sorption by the Ca systems than the K systems and decreased sorption with increasing pH suggests that cation bridging and cation exchange contribute to sorption. X-ray diffraction analysis showed that TC and CTC were sorbed in the interlayers of smectites and that the presence of HS reduced interlayer sorption of tetracyclines by smectites in clay-HC. The results indicate that tetracyclines are dominantly sorbed on soil clays and that HS in clay-HC either mask sorption sites on clay surfaces or inhibit interlayer diffusion of tetracyclines.  相似文献   

10.
Most of the thermodynamic models available in the literature describing the speciation of the calcite surface do not predict a significant concentration of sorbed Ca(II), whereas previous electrokinetics studies clearly show that Ca(2+) is the main cation determining the potential of the calcite surface. This study proposes a new thermodynamic model based on ion-exchange theory that is able to describe the reversible sorption of Ca(2+) on calcite. To constrain the model, concentrations of Ca(II) sorbed reversibly on the mineral surface were obtained as a function of pH. Such experimental data were obtained using solutions in equilibrium with both calcite and fixed p(CO2(g)) values (from 10(-5) to 10(-2) atm). The concentration of (de)sorbed Ca(II) is almost constant in the [7-9.5] pH range, having a value of approximately 1.2 × 10(-6) ± 0.4 × 10(-7) eq·g(-1). Such a value agrees with total sorption site densities that were previously calculated by crystallography and is used to obtain a selectivity coefficient between H(+) and Ca(2+) species by fitting the experimental data. Then, selectivity coefficients between H(+) and different metallic cations (Zn(2+), Cd(2+), Pb(2+)) that are able to accurately describe previously published data are proposed. Finally, the model is used to predict the contribution of calcite in the overall sorption of Cd(II) on a natural and complex solid (calcareous aquifer sand).  相似文献   

11.
Copper retention by ferrihydrite, leaf compost, and montmorillonite was studied over 8 months in systems that emulate a natural soil where different solid phases compete for Cu through a common solution in a compartmentalized batch reactor. Copper speciation in solution (total dissolved, DPASV-labile, and free) and exchangeable and total Cu in individual solid phases were determined. Organic carbon in solution (DOC) and that retained by the mineral phases were also determined. Cu sorption reached steady-state after 4 months and accounted for 80% of the Cu initially added to the system (0.15 mg L(-1)). The remaining 20% stayed in solution as nonlabile (82.8%), labile (17%), and free (0.2%) Cu species. Copper sorption followed the order organic matter > silicate clays > iron oxides. Within each solid phase, exchangeable Cu was < or = 10% of the total Cu sorbed. DOC reached steady state (22 mg L(-1)) after 4 months and seemed to control Cu solubility and sorption behavior by the formation of soluble Cu-DOC complexes and by sorbing onto the mineral phases. DOC sorption onto ferrihydrite prevented Cu retention by this solid phase. Using a multicomponent system and 8 months equilibrations, we were able to capture some of the more important aspects of the complexity of soil environments bytaking into account diffusion processes and competition among solid- and solution-phase soil constituents in the retention of a metal cation.  相似文献   

12.
This paper discusses the modeling of anion and cation leaching from complex matrixes such as weathered steel slag. The novelty of the method is its simultaneous application of the theoretical models for solubility, competitive sorption, and surface precipitation phenomena to a complex system. Selective chemical extractions, pH dependent leaching experiments, and geochemical modeling were used to investigate the thermodynamic equilibrium of 12 ions (As, Ca, Cr, Ba, SO4, Mg, Cd, Cu, Mo, Pb, V, and Zn) with aqueous complexes, soluble solids, and sorptive surfaces in the presence of 12 background analytes (Al, Cl, Co, Fe, K, Mn, Na, Ni, Hg, NO3, CO3, and Ba). Modeling results show that surface complexation and surface precipitation reactions limit the aqueous concentrations of Cd, Zn, and Pb in an environment where Ca, Mg, Si, and CO3 dissolve from soluble solids and compete for sorption sites. The leaching of SO4, Cr, As, Si, Ca, and Mg appears to be controlled by corresponding soluble solids.  相似文献   

13.
Several wines were analyzed by high-performance liquid chromatography (HPLC-PDA), inductively coupled plasma mass spectrometry (ICP-MS), and flame atomic absorption spectroscopy (FAAS) in order to associate the concentration levels of the chemical parameters with the geographical origin of wines and wine varieties. Thus, the concentrations of 22 elements (Li, Be, Co, Ni, Cs, U, Pb, V, As, Ba, Cr, Cu, Zn, Al, Mn, Rb, Sr, Fe, Ca, Mg, Na, and K) and seven phenolic compounds (gallic acid, (+)-catechin, (?)-epicatechin, p-coumaric acid, ferulic acid, trans-cinnamic acid, and resveratrol) were analyzed in 22 wines from two different wine-producing areas of Romania. Among the phenolic compounds, (+)-catechin, (?)-epicatechin, p-coumaric acid, ferulic acid, and resveratrol concentrations were the most useful markers for wine differentiation by geographical origin and wine variety, whereas Ba, Be, Cr, Cs, Li, Mg, Na, Ni, Sr, U, and Zn were the main inorganic parameters selected. To explore the distribution pattern of the samples, aimed at differentiating the wine samples by geographical region and wine variety, principal component analysis (PCA) was applied to the obtained data.  相似文献   

14.
Competitive ion-exchange reactions were studied on a strong-base anion-exchange resin to remove NO3- and uranium from a contaminated groundwater containing high levels of NO3- (approximately 140 mM), SO4(2-) (approximately 10 mM), and U(VI) (approximately 0.2 mM). Results indicate that although SO4(2-) carries divalent negative charges, it showed the least selectivity for sorption by the Purolite A-520E resin, which is functionalized with triethylamine exchange sites. Nitrate was the most strongly sorbed. Sorption selectivity followed the order of NO3- > Cl- > SO4(2-) under the experimental conditions. Nitrate competitively sorbed and displaced previously sorbed SO4(2-) in a column flow-through experiment and resulted in a high elution front of SO4(2-) in the effluent. Although the concentration of uranium in groundwater is orders of magnitude lower than that of NO3- or SO4(2-), it was found to be strongly sorbed by the anion-exchange resin. Because the most stable uranium species in oxic and suboxic environments is the UO2(2+) cation, its strong sorption by anion-exchange resins is hypothesized to be the result of the co-ion effect of NO3- by forming anionic UO2(NO3)3- complexes in the resin matrix. These observations point out a potential alternative remediation strategy that uses strong-base anion-exchange resins to remove uranium from this site-specific groundwater, which has a low pH and a relatively high NO3- concentration.  相似文献   

15.
Nitroaromatic compounds (NACs) are prominent soil and sediment contaminants that are strongly adsorbed by smectites at extents that depend on hydration properties of the exchangeable cation. Potassium smectites adsorb nitroaromatics much more strongly than calcium smectites, so that adjustment of K+ versus Ca2+ occupation on cation exchange sites in smectites can be used to modulate the retention and release of nitroaromatics. We suggest that this modulation can be used to advantageously manage the bioavailability and toxicity of NACs during bioremedation. We have measured the toxicity of 2,4-dinitrotoluene (2,4-DNT) to duckweed grown in smectite suspensions and utilized Ca2+/K+ exchange to retain or release 2,4-DNT. Retention by potassium smectite reduced bioavailability and hence toxicity to duckweed. Addition of Ca2+ to replace K+ by ion exchange released adsorbed 2,4-DNT, which is toxic to duckweed. So smectites can be used to sequester or release 2,4-DNT predictably and provide means to control bioavailability and environmental toxicity.  相似文献   

16.
Mass balance studies at a number of calibrated watersheds in eastern North America suggest that large losses of Ca from soil have occurred due to acid deposition. However, there is considerable controversy over whether losses have occurred from the exchangeable pool or whether there are other sources of Ca that have not been considered. Mass balance calculations at a small, calibrated catchment (PC1) in south-central Ontario also indicate that large losses of Ca have occurred over the past 2 decades. If the exchangeable Ca pool has declined by approximately 40% between 1983/1984 and 1998/1999 but the exchangeable Mg pool has remained relatively stable, these changes should be evident in streamwater chemistry. The slope of the buffer curve relating Ca to (sigma)acid anions (F(Ca)) decreased significantly over the study period. We estimate that F(Ca) decreased by 12-24% between 1983 and 1999, although the level of decrease is affected by changes in hydrology. During the same period, there was no significant change in F(Mg), and the annual volume-weighted Ca:Mg (equiv/equiv) ratio in streamwater decreased from approximately 2.8 to approximately 2.1. Measured changes in streamwater chemistry translate into Ca losses from the exchangeable pool of approximately 250-570 mequiv/m2 over the study period, which is similar to estimated losses based on soil measurements (approximately 425 mequiv/m2) and mass balance calculations (approximately 380-430 mequiv/m2). The magnitude of Ca loss cannot be explained by decreases in Ca deposition or decreased Ca weathering. Large Ca losses from the soil exchangeable pool have serious implications for future forest health and the recovery of streamwater from acid deposition.  相似文献   

17.
A study on the individual sorption of Cr(III), Cu, and Zn on polymerin, the humic-acid-like fraction of olive mill wastewater, and its derivatives, K-polymerin and an Fe(OH)x-polymerin complex, showed that these heavy metals were strongly sorbed on polymerin and K-polymerin in the order Cr(III) > Cu > Zn. The sorption on Fe(OH)x-polymerin was to a lower extent compared with that of the other two sorbents, but to a higher extent compared with ferrihydride [Fe(OH)x]. Combined atomic absorption spectrometry and diffuse reflectance infrared Fourier transform spectroscopy analyses showed that the selected heavy metals were individually sorbed on polymerin by means of a cation exchange mechanism, which was consistent with the replacement of Ca, Mg, K, and H bound to the carboxylate groups of the biosorbent and the concomitant chelation of the heavy metals by the OH groups of polymerin polysaccharide component. In binary combination and equimolar ratio, Cu was sorbed by polymerin more selectively than Zn. In ternary combination and equimolar ratio, Cr(III), Cu, and Zn were sorbed by polymerin in the order Cr(III) > Cu > Zn. The sorbing capacity of Zn and Cu was strongly influenced by Cr(III), whereas the sorbing capacity of Cr(III) was not affected bythe presence of the other two metals. The overall sorbing capacity of the binary and ternary mixtures of the three metals on polymerin proved to be considerable and much greater than that on Fe(OH)x-polymerin. Simulated wastewaters contaminated with Cu and Zn were purified after three sorption cycles by polymerin renewed at each cycle, whereas those containing a mixture of Cr(III), Cu, and Zn showed residues of Zn after five cycles. We briefly discuss environmental and industrial advantages for a possible exploitation of polymerin.  相似文献   

18.
Heavy metal sorption at the muscovite (001)-fulvic acid interface   总被引:2,自引:0,他引:2  
The role of fulvic acid (FA) in modifying the adsorption mode and sorption capacity of divalent metal cations on the muscovite (001) surface was evaluated by measuring the uptake of Cu(2+), Zn(2+), and Pb(2+) from 0.01 m solutions at pH 3.7 with FA using in situ resonant anomalous X-ray reflectivity. The molecular-scale distributions of these cations combined with those previously observed for Hg(2+), Sr(2+), and Ba(2+) indicate metal uptake patterns controlled by cation-FA binding strength and cation hydration enthalpy. For weakly hydrated cations the presence of FA increased metal uptake by approximately 60-140%. Greater uptake corresponded with increasing cation-FA affinity (Ba(2+) ≈ Sr(2+) < Pb(2+) < Hg(2+)). This trend is associated with differences in the sorption mechanism: Ba(2+) and Sr(2+) sorbed in the outer portion of the FA film whereas Pb(2+) and Hg(2+) complexed with FA effectively throughout the film. The more strongly hydrated Cu(2+) and Zn(2+) adsorbed as two distinct outer-sphere complexes on the muscovite surface, with minimal change from their distribution without FA, indicating that their strong hydration impedes additional binding to the FA film despite their relatively strong affinity for FA.  相似文献   

19.
As a low-soluble phosphate mineral capable of binding various metal ions, apatite can be used to immobilize toxic metals in soils and waters. In the present research the factors affecting sorption and desorption of Cd2+ and Zn2+ ions on/from apatites are investigated. Batch experiments were carried out using synthetic hydroxy-, fluoride-, and carbonate-substituted apatites having various specific surface area (SSA). Apatite sorption capacity was found to depend mainly on its SSA, ranging from 16 to 78 and from 11 to 79 mmol per 100 g of apatite for Cd2+ and Zn2+, respectively. The solution composition (pH, and presence of Cl- and NO3- ions) had no essential impact on sorption. Desorption of bound cations depended both on the sorption level and solution composition. The amount of desorbed Cd2+ and Zn2+ increased proportionally to the amount of sorbed cations. However, apatites having higher sorption capacity release relatively less sorbed cations. Desorption increases with increasing Ca2+ concentration in the solution, reaching 8-20% of sorbed Cd2+ in 0.002 M, 10-35% in 0.01 M, and 33-45% in 0.05 M Ca(NO3)2 solution. Compared to nitrate solutions, the presence of Cl- ions in the solution promotes the release of bound cations. Desorption of Zn2+ is slightly higher than that of Cd2+. The desorption mechanism was assumed to include both ion-exchange and adsorption of Ca2+ ions on apatite surface.  相似文献   

20.
《Food chemistry》2005,92(2):305-309
Avocado honey samples were analyzed by inductively coupled plasma optical emission spectrometric. First, the botanical origin of the honeys was confirmed by melissopalynological analysis. Twenty-four minerals were quantified for each honey sample. The elements Al, Ba, Ca, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, S, Se, Si and Zn were detected in all samples; seven elements were very abundant (Ca, K, Mg, Na, P, S and Si), six were not abundant (Al, Cu, Fe, Li and Zn) and 11 were trace elements (As, Ba, Cd, Co, Cr, Mo, Ni, Mo, Pb, Se, Sr and V).  相似文献   

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