Rare earth elements determination and distribution patterns in surface marine sediments of the South China Sea by INAA,Malaysia

Results obtained from the analysis of sediments surface samples taken from rivers mouth and polluted marine environment were analyzed for REE contents to determine the concentrations of La, Ce, Sm, Eu, Tb, Dy, Lu and Yb using instrumental neutron activation analysis. Thirty surface samples were collected from ten sites in the coastal marine sediments of the South China Sea along 957 km stretch of the east coast of Peninsular Malaysia. The samples prepared in the powdered form before irradiating them in a neutron flux of ~4 × 10¹² n cm⁻² s⁻¹ at 750 kW power using the TRIGA Mark II research reactor at Malaysian Institute for Nuclear Technology (MINT). Results of the total concentration are used to establish baseline data in environmental pollution assessment and to develop the correlations between the Ce/Ce* anomalies and the distribution patterns of some the light rare earth elements (LREEs) and the heavy rare earth elements (HREEs). The Chondrite-normalized REE pattern from each site examined and used to explain the sedimentation patterns by anthropogenic activities and by natural processes such as shoreline erosion, weathering deposits. Shale-normalized (NASC) patterns suggest enrichment of LREEs relative to the HREEs with a positive Ce/Ce* anomaly. Validation of the used method was done using a Soil-7 SRM.     

Sedimentation pattern and sediments bioavailability in a wastewater discharging area by sequential metal analysis

Atomic absorption spectrometry was applied to investigate sedimentation pattern and sediments bioavailable phase (BAP) at 41 sites of a wastewater discharging area. The position of sampling sites was confirmed by the aid of a global positioning system (GPS). Contaminants discharged from a large wastewater plant are dispersed to the inner bay and the coastal line rather than the outer bay and the center waterway. The fractional composition of sediment Zn in the discharging area accounted for the presence of exchangeable 239 mg/kg (35.1%)>reducible 163 mg/kg (24.0%)>carbonate 149 mg/kg (22.0%)>residual 98 mg/kg (14.4%)>organic 31 mg/kg (4.6%) in sediment layers of 0–2 cm. However, the order was changed in layers of 15–20 cm as residual>reducible>organic>carbonate>exchangeable. The most abundant fraction of sediment Cu and Fe was organic Cu and residual Fe, respectively. The content of BAP in sediments are quite different with respect to metal species and sediment layer analyzed. It is obvious that sequential metal analysis is a useful tool in understanding dispersion of sediments and sedimentation patterns.     

Correlation between chemical composition and radical scavenging activity of 10 commercial essential oils: Impact of microencapsulation on functional properties of essential oils

A comparative study was carried out on the essential oils of 10 aromatic plants that are extensively used in Egypt for their distinctive aroma and functional properties. Each essential oil (EO) was characterized by means of gas chromatography-mass spectrometry (GC–MS) analysis and evaluated for its radical scavenging activity by 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2-azinobis (2-ethyl-benzolhiaxoline-6-sulfonic acid)(ABTS) assays. The phenolic content of the 10 EOs was in the descending order: clove > thyme > majoram > basil > anise > chamomile > cinnamon > dill > ginger > rosemary. The radical scavenging activity of the EOs was correlated to the presence of phenolic compounds, such as eugenol, thymol, carvacrol and trans-anethol, or the synergism between the antioxidant activity of nonphenolic compounds such as terpinene-4-ol, α-terpinene, curcumene and chamazulene. Clove essential oil exhibited the highest oil content and radical scavenging activity so it was encapsulated, separately, in three coating materials. Sodium alginate showed the highest retention, encapsulation efficiency and loading capacity of clove EO. Microencapsulation in sodium alginate and chitosan improved the antioxidant activity and phenolic content of the encapsulated clove EO compared with carboxymethyl cellulose. The results support the possibility of using the encapsulated EOs as natural and easy handle antioxidants.     

Speciation of rare earth elements in soil by sequential extraction then HPLC coupled with visible and ICP-MS detection

The distribution of rare earth elements (REE) in a pooled soil sample collected from Zhangzhou, Fujian Province, China, was screened by a five-step sequential extraction procedure coupled with ICP–MS determination after preconcentration of REE and removal of the matrix by extraction with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HPMBP). The results showed that the distribution of REE in the different fractions of the pooled soil sample studied followed the order soluble species (46.76%) > species bound to organic matter (22.08%) > species in the residue (16.77%) > species bound to Fe–Mn oxides (2.02%). An effective method for speciation of REE, which utilized weak cation-exchange HPLC separation hyphenated with post-column derivatization and visible or on line ICP–MS detection, was, moreover, developed and successfully applied to the speciation of REE in the soluble extract of the pooled soil sample. The stability of known complexes of lanthanum during the HPLC separation was investigated with fluoride, citrate, and ethylenediamine tetraacetic acid (EDTA) chosen as ligands modeling those in the soil. REE in the soluble extract of the pooled soil sample were subsequently classified into three types of species –≤ + 1 charged complexes (negatively charged, neutral, and +1 charged), + 2 charged complexes, and “free” REE species. This method is expected to be useful for identification of bioavailable (or toxic) species of REE in environmental samples. Received: 14 November 2000 / Revised: 26 January 2001 / Accepted: 30 January 2001     

Amazon estuary — assessment of trace elements in seabed sediments

The interactive processes operating on the continental shelf adjacent to the river mouth control the amount and the characteristics of the Amazon discharge reaching the Atlantic Ocean. In this study, the distribution of trace elemental concentrations, with emphasis to the rare-earth elements, in sediment cores collected at several stations from the Amazon continental shelf during the falling water period was investigated by instrumental neutron activation analysis. Cores from the terrigenous and blue water zones have relatively uniform REE concentrations throughout the profile. Cerium anomalies for samples of the upper section of the eight stations are consistently positive and of high values (normally >2). Similar variation in the elemental concentration ratios between the seabed sediments and Amazon River suspended sediments was seen for stations located in the biogenic and blue water zones, with an enrichment for Ce, Sm, Fe, Th, and Sc and a depletion for the La, Eu, Tb, Yb, Co, Cr, Cs, Hf, Ta, and Zn. The shale-normalized REE patterns from shelf sediments are enriched in LREE relative to HREE, with enrichment factors varying from 1.5 for stations near the river mouth (terrigenous zone) to 1.9 for stations located far in the blue water zone. Published data for the Amazon River suspended sediment agree remarkably well with this observation of LREE-enrichment.     

One hundred and forty years “Fresenius’ Journal of Analytical Chemistry”

The distribution of rare earth elements (REE) in a pooled soil sample collected from Zhangzhou, Fujian Province, China, was screened by a five-step sequential extraction procedure coupled with ICP–MS determination after preconcentration of REE and removal of the matrix by extraction with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HPMBP). The results showed that the distribution of REE in the different fractions of the pooled soil sample studied followed the order soluble species (46.76%) > species bound to organic matter (22.08%) > species in the residue (16.77%) > species bound to Fe–Mn oxides (2.02%). An effective method for speciation of REE, which utilized weak cation-exchange HPLC separation hyphenated with post-column derivatization and visible or on line ICP–MS detection, was, moreover, developed and successfully applied to the speciation of REE in the soluble extract of the pooled soil sample. The stability of known complexes of lanthanum during the HPLC separation was investigated with fluoride, citrate, and ethylenediamine tetraacetic acid (EDTA) chosen as ligands modeling those in the soil. REE in the soluble extract of the pooled soil sample were subsequently classified into three types of species –≤ + 1 charged complexes (negatively charged, neutral, and +1 charged), + 2 charged complexes, and “free” REE species. This method is expected to be useful for identification of bioavailable (or toxic) species of REE in environmental samples.     

印度洋热液区贻贝及栖息沉积物中金属元素的特征分析

本研究采集了印度洋热液区贻贝生物及其栖息沉积物样品,分析了生物体及沉积物中常见微量元素及稀土元素的含量与分布特征,研究了生物体与沉积物金属元素的相关性,以及稀土元素的生态化学特征等.结果表明:印度洋热液区沉积物中常见微量金属主要为Fe(96.62 mg/kg)、Mn(1.143 mg/kg)和Zn(322.6 μg/kg),微量元素归一化计算得Fe含量比值高达98.15%,可获悉该热液区沉积物主要为铁矿类物质.深海贻贝中微量元素及稀土元素的分布趋势与深海沉积物中元素分布存在较好的相关性,相关性系数分别为0.991与0.996,近海贻贝中金属元素的含量及分布与深海贻贝存在差异性.深海沉积物与贻贝中轻重稀土元素均呈现分馏现象,且贻贝中富集轻稀土比较显著;从稀土配分模式可知,沉积物与贻贝中的Eu与Gd均呈现异常现象,深海沉积物和深海贻贝中Eu异常现象较为显著.深海沉积物、贻贝及近海贻贝中δEu分别为9.50、10.68和0.23,而δCe分别为2.21、2.71和4.38,表明近海贻贝中稀土元素富集来源与深海贻贝存在差异性,深海沉积物与深海贻贝稀土元素具有同源性.     

A contribution to the evaluation of REE in an Egyptian phosphate deposit

Results are presented of ICP-AES determinations of 13 rare earth elements (REE), Sc and Y in 47 core samples of 10 bore holes in the phosphate deposit of the Abu-Tartur area, Western Desert, Egypt. The complete dissolution of the samples was achieved by digestion with HF/HNO₃/HCl in a closed PTFE decomposition vessel. Such analytical lines were selected that showed no spectral interferences from the major constituents of the phosphate samples or from other REE in the samples. The precision for the determination of the individual elements for the whole procedure ranges from 0.8% to 4.0%. Also, smooth normalized chondrite and shale patterns were obtained. The results revealed that the total REE content in the investigated samples was between 0.8 and 2 mg/g, which is remarkably high when compared with many phosphate deposits in other parts of the world. The results also showed that the concentrations of individual REE as well as their total concentrations in the samples follow their P₂O₅ content, indicating that the REE may be accumulated within the phosphate fraction of the phosphate bearing sediments.Presented at the Rare Earth Minerals Conference, London (UK), April 1 and 2 (1993)     

Concentrations of rare earth elements in sediments,mussels and fish from a Danish marine environment,Lillebaelt

Results for the content of the rare earth elements (REE), La, Ce, Nd, Sm, Eu, Tb, Yb and Lu in sediments, mussels and fish are presented for an area polluted by REE. The REE are emitted with the process waste water stream from a fertilizer production plant. The method of analysis has been INAA. An attempt to combine the INAA with a simple destruction/preconcentration method is described.     

Effect of processing on the release of phenolic compounds and antioxidant activity during in vitro digestion of hulless barley

Hulless barley contains phenolic compounds and possesses various antioxidant activities. To clarify the effects of thermal processing and in vitro digestion on the release of phenolic compounds in hulless barley, we studied the phenolic components and antioxidant activities of hulless barley after steaming, roasting processes, and in vitro digestions. Both total phenolic content (TPC) and total flavonoid content (TFC) in raw hulless barley (HB, 4.14 mg/g DW and 1.53 mg/g DW, respectively) were higher than that of steamed hulless barley (SHB) and roasted hulless barley (RHB). In vitro digestion significantly released more ferulic acid from its bound form, but hydrolyzed some amount of flavonoid (luteolin). Chrysoeriol-7-O-glucouronide was significantly detected (412.13 µg/g DW in HB, 382.19 µg/g DW in SHB, and 396.91 µg/g DW in RHB) in all three hulless barley. The total released content of phenolic compounds obtained from each phase after digestion reached to 46% and 45% for SHB and RHB, which was higher than that in the HB (41%). The antioxidant assay (via DPPH and ABTS free radical scavenging assays) indicated that the capacity of HB was obviously higher than that of SHB and RHB in undigested group. For digested group, the ABTS⁺ assay order was following, undigested > oral > small intestine > gastric > large intestine. The DPPH assay results indicated the antioxidant capacity as the order of undigested > oral > gastric > large intestine. Correlation analysis showed that ferulic acid, chrysoeriol-7-O-glucouronide, luteolin, chrysoeriol, and luteolin-7-O-glucouronide contributed to the antioxidant activities. Hierarchical cluster analysis (HCA) grouped samples accordingly. Roasting process could be considered as a better daily thermal treatment for hulless barley than steaming in terms of phenolic compounds and their antioxidant activities.     

Bioextraction of heavy metals from colloidal sludge systems

Chemical (acidic) and biological (under the action of acidogenic metabolites synthesized by microorganisms present in a sediment) extraction of heavy metals from colloidal sludge sediments produced at a wastewater biochemical treatment plant is studied. It is established that both methods provide at least 80% extraction of heavy metals, which decreases in the sequence Zn > Mn > Cu > Ni > Co > Pb > Cr. The advantage of the biological procedure is the possibility of using the processed sludge sediments, which contain many useful components, as fertilizers.     

Metals in water and surface sediments from Henan reaches of the Yellow River, China

The concentrations of Cd, Cr, Cu, Ni, Pb and Zn were determined in the water and surface sediments from the Henan reaches of the Yellow River. Twenty-three sampling sites along the Yellow River and its tributaries were selected. Generally, metal concentrations were found to decrease in sequences of Zn > Cu > Pb > Cr > Ni > Cd in water and Zn > Cr > Pb > Ni > Cu > Cd in sediments. High levels of metal concentration were determined at a few stations of the river and its tributaries, such as Yiluo River, Si River and Qin River. The pollution of the Yellow River by Cd, Cr, Cu, Ni, Pb and Zn can be regarded as much higher compared to the background values, US EPA criteria (1999) and China water quality criteria (2002). For sediments, metal levels except Pb did not significantly exceed the average shale levels and backgrounds in several countries including China. Data analysis manifests that positive correlations were found between Cu, Ni and Zn in water, and Pb, Ni, Zn and Cr in sediments. The Pearson correlation coefficient analysis and Cluster analysis were provided to assess the possible contamination sources. The results indicate a general appearance of serious pollution along the banks of the Yellow River. The wastewaters discharged by the mine plants, smelter plants, power plants, battery plants, tannery plants, etc., and sewage inputs from the cities along the river banks may be the sources of metals.     

Precise measurement of the hyperfine splitting and isotope shift of8S7/2→10P9/2 transition in241Am and243Am atoms

The study of physico-chemical and biotic processes in the environment is essential to understanding the behavior of transuranic nuclides and to assess their environmental impact. Dialysis, ion exchange, and co-precipitation techniques have been used to study speciation. The dissolved fraction of^239,240Pu in coastal waters of Bombay harbor bay and in interstitial water from bottom sediments of the bay were found to be associated with organic matter. The desorption of Pu from sediments in coastal waters is influenced by salinity and carbonate. Studies indicate that, even from anoxic sediments, remobilization and the potential for migration is not significant.     

Subcellular and molecular localization of rare earth elements and structural characterization of yttrium bound chlorophyll a in naturally grown fern Dicranopteris dichotoma

A rare earth element (REE) hyperaccumulator, Dicranopteris dichotoma, sampled from an REE mining area in South-Jiangxi region, was chosen for analysis of 15 REEs at subcellular and molecular levels by inductively coupled plasma-mass spectrometry (ICP-MS). The sum of the concentrations of 15 REEs (∑REEs) of D. dichotoma leaf was about 0.1% dry mass. Results indicated that the ∑REEs of different subcellular fractions of D. dichotoma leaf were cell walls>organelles>the ‘soluble’ fraction (i.e., cytosol and vacuoles)>cell membranes. ICP-MS results also showed that REEs existed in chlorophylls and lutein, though REE concentrations in carotene and pheophytin were both lower than the procedural blank levels. The ∑REEs of crude lipopolysaccharide and Ribulose 1,5-bisphosphate carboxylase/oxygenase (Rubisco) obtained from D. dichotoma leaf were 1200 and 343 mg/kg, respectively. The extended X-ray absorption fine structure (EXAFS) study of D. dichotoma chlorophyll a indicated that yttrium was bound to the porphyrin ring of chlorophyll a, and one yttrium atom was surrounded by four nitrogen atoms with the average yttrium-nitrogen bond length being 0.236 nm. These data might be useful for understanding of the physiological role of REEs in hyperaccumulator D. dichotoma.     

Rare earth elements determination and distribution patterns in sediments of a polluted marine environment by instrumental neutron activation analysis

Results obtained from the analysis of sediment core samples taken froma fairly polluted marine environment were analyzed for the REE contents todetermine the concentrations of La, Ce, Sm, Eu, Tb, Dy and Yb using instrumentalneutron activation analysis. Core samples were divided into strata of between2 to 3 cm intervals and prepared in the powdered form before irradiating themin a neutron flux of about 5.0 . 10¹² n . cm ^—2s ^—1 in a Triga Mark II reactor. Down-core concentration profilesof La, Ce, Sm, Eu, Tb, Dy and Yb in 3 core sediments from three sites areobtained. The shale-normalized REE pattern from each site was examined andlater used to explain the history of sedimentation by natural processes suchas shoreline erosion and weathering products deposited on the seabed and furnishingsome baseline data and/or pollution trend occurring within the study area.The shale-normalized REE patterns also showed that LREE in the sediment samplesexhibit enrichment relative to HREE particularly, La and Sm showing enrichmentcompared to the ratios in shale. REE concentrations of 124 µg/g at thesurface of sediment collected at two of the three sites were found to decreaseto 58 and 95 µg/g, respectively. This was of particular interest whenit is used to explain the anomalies occurring in the marine sediment as aresult of geochemical processes over a long period of time. Changes in concentrationsfrom surface to bottom of the sediments ratioed to Sm concentrations and thecorrelation between concentrations of Sm and these elements were also investigatedand correlation coefficients were calculated for all REEs and sites. Validationof the method used was done using a Soil-7 SRM.     

Distribution of rare earth elements in the estuarine and coastal sediments of the Daliao River System, China

The Daliao River System (DRS) estuary in Liaodong Bay features a highly industrial, urbanized, and agricultural catchment. The objective of this study was to determine the content, behavior, and distribution of the rare earth elements (REEs) in the estuarine and coastal sediments. To this end, 35 sediment samples were collected from the estuarine and coastal area and analyzed for REEs, Fe, Al, and Mn. The mean concentrations in mg kg^?1 of the sediments were 33.4 (La), 64.1 (Ce), 7.9 (Pr), 29.0 (Nd), 5.4 (Sm), 1.2 (Eu), 4.2 (Gd), 0.78 (Tb), 4.0 (Dy), 0.84 (Ho), 2.3 (Er), 0.40 (Tm), 2.3 (Yb), and 0.37 (Lu). The REE concentrations in the sediments were significantly correlated with one another (r ²  = 0.959–0.988) and the concentrations of Fe, Al, and Mn (r ²  = 0.768–0.870). The total concentration ∑REE ranged from 73.5 to 203.5 mg kg^?1, with an average of 156.0 mg kg^?1 being observed, and generally higher in the estuarine sediments than in the coastal sediments, most likely due to the salt-induced coagulation of river colloids and subsequently their accumulation at the estuarine bottom. The ratio of light REEs (∑LREE) to heavy REEs (∑HREE) was 9.4. Chondrite-normalized REE distributions were observed to be similar for the estuarine and coastal sediments, riverine suspended particles, and watershed soils of the DRS with higher LRRE enrichment than HREE and greater Eu depletion than Ce depletion. These results demonstrate that neither geochemical processes that carry soils to estuarine sediments nor long-term industrial and agricultural activities alter the distribution or fractionation of the REEs in the study area.     

Rare earth elements,thorium and uranium in ores of the North-Latium (Italy)

In geochemistry, the distribution of the Rare Earth Elements (REEs) in earth crust and mantle allows to understand geochemical cycles and origin and age of igneous rocks. In this article REEs (Ce, Dy, Eu, La, Nd, Sm, Tb, and Yb), Th and U in ores of the North-Latium (Bracciano area, Ceriti Mt., Fate Mt., Sabatini Mt., Vulsini Mt., Acqua Rossa basin), have been investigated for evaluating the extraction feasibility for industrial applications. 107 samples were irradiated in the rotating rack of the TRIGA Mark II reactor of the R.C. Casaccia (ENEA) at neutron flux of 2.6 × 10¹² n × cm⁻² × s⁻¹ for 12 h together with primary and secondary standards. The gamma spectrometry measurements were performed after 8 h, 3 and 30 days of decay by means of HPGe detector (FWHM 1.75 keV at 1332.5 keV, peak/Compton ratio 55.1, relative efficiency of 22%) connected to a multi-channel analyzer. The total REE mean content is 105 μg g⁻¹, ranging widely between 2.23 and 410.5 μg g⁻¹ (average coefficient of variation 112%). A similar behavior is found for Th and U: their average levels are 13.5 and 6.0 μg g⁻¹, respectively. A quite good correlation between REEs and Th (and U) is found for Ceriti Mt. (r ² > 0.8) whereas for the other areas the correlation is <0.7. The results obtained evidence the low U content in the investigated locations.     

Physicochemical features and antioxidant activity of polysaccharides from Herba Patriniae by gradient ethanol precipitation

Four polysaccharides BJP50, BJP60, BJP70 and BJP80 (total named BJPs) were separated from Herba Patriniae via gradient ethanol precipitation with 50%, 60%, 70% and 80%, respectively. After decolorization and deproteinization, their physicochemical features and antioxidant activities were investigated. The results showed that the total sugar content of BJPs accounted above 50% but no protein contained, while BJP50 and BJP60 contained a small amount of uronic acid. GC analysis indicated that BJPs were mainly composed of galactose, arabinose, glucose, mannose, xylose and rhamnose. From BJP50 to BJP80, the types of monosaccharides and the content of arabinose, glucose and mannose increased but that of galactose and rhamnose decreased, and their molecular weights gradually reduced from 2.3 × 10⁶ to 4.5 × 10³. BJPs had a good thermal stability with the order of BJP80 > BJP70 > BJP60 > BJP50. The vitro bioactivity assay showed that BJP80 and BJP70 exhibited stronger scavenging capacities for DPPH, ABTS and hydroxyl free radicals than that of BJP60 and BJP50. As the concentration reached 4 mg/mL, the scavenging capacities of BJP80 and BJP70 on DPPH and hydroxyl free radical were up to 92% and 95%, respectively, and their antioxidant activities gradually approached to the positive control.