Application of LiMgPO4 crystal for proton beam quality control in radiotherapy.

The radioluminescence (RL) emitted by LiMgPO4 detector under proton beam irradiation was investigated in real time at the radiotherapy facility in the Institute of Nuclear Physics Polish Academy of Sciences in Krakow. The facility uses protons accelerated by the AIC-144 isochronous cyclotron up to the energy of 60 MeV. The measurements of RL were carried out using a remote optical fiber device with a luminophore detector and photomultiplier located at opposite ends of the optical fiber. A thin slice of LiMgPO4 doped with Tm (1.2 mol%) crystal was exposed to the proton beam. The tested detector allowed for the measurement of proton beam current, flux fluence and determination of proton beam time structure parameters. The investigation of LiMgPO4 crystal showed its high sensitivity, fast reaction time to irradiation and possibility of application as the detector for control of proton beam parameters.

Selected Essential and Toxic Chemical Elements in Hypothyroidism-A Literature Review (2001-2021).

Thyroid hormones are known for controlling metabolism of lipids, carbohydrates, proteins, minerals, and electrolytes and for regulating body temperature. Normal thyroid status depends on the chemical/elemental composition of body fluids and tissues, which changes depending on physiological state, lifestyle and environment. A deficiency or excess of certain essential chemical elements (selenium, zinc, copper, iron or fluorine) or exposure to toxic (cadmium or lead) or potentially toxic elements (manganese or chromium) interacts with thyroid hormone synthesis and may disturb thyroid homeostasis. In our review, accessible databases (Scopus, PubMed and Web of Science) were searched for articles from 2001-2021 on the influence of selected chemical elements on the development of hypothyroidism. Our review adopted some of the strengths of a systematic review. After non-eligible reports were rejected, 29 remaining articles were reviewed. The review found that disruption of the physiological levels of elements in the body adversely affects the functioning of cells and tissues, which can lead to the development of disease.

Seaweeds rehydration and boiling: Impact on iodine, sodium, potassium, selenium, and total arsenic contents and health benefits for consumption.

Considering the importance of seaweeds for the development of sustainable and innovative food products, this study aimed to characterize the impact of hydrothermal processing on iodine, sodium, potassium, selenium, and arsenic concentrations of four seaweed species (S. latissima, L. digitata, U. pinnatifida, and C. crispus) and on the associated health risks-benefits for consumers. These elements revealed a common pattern for leachable fractions of iodine, total arsenic, and selenium: L. digitata ≥ S. latissima > C. crispus > U. pinnatifida after rehydration and boiling during different periods. The behavior for sodium was: S. latissima > L. digitata > C. crispus > U. pinnatifida, and for potassium: U. pinnatifida > L. digitata > S. latissima > C. crispus. Generally, the species that attained more significant losses were S. latissima and L. digitata. A health-relevant sodium/potassium ratio below 0.7 was found for all species except for U. pinnatifida. In some species, the risk-benefit analysis revealed that high iodine and arsenic levels might promote risks for consumption, even after 20 min boiling, but 5 g of processed U. pinnatifida could contribute to adequate iodine, sodium, potassium, and selenium intakes for all population groups. Standardized processing treatments of seaweeds can open new opportunities for the sector.

Statistical analysis and susceptibility properties of heavy/light metal pollution in surface seawater of Izmir Bay.

The inner bay of Izmir is known as the part between Sasali/Karsiyaka coastline and Güzelbahçe/Bayrakli. It is used extensively in transportation. There is constant ferry transportation and an international port operates in this region. There are also a few streams that flow into the inner bay. Therefore, the inner bay can be exposed to continuous chemical pollutants, and these wastes can intensively be observed in its natural structure. In this study, the magnetic susceptibility values and elemental analyses of the samples taken from the surface sea waters of the inner bay coastline were performed. Silicon, strontium, and manganese elements were mostly observed in the samples. The greatest susceptibility values were seen in the Bostanli ferry port and Göztepe ferry. In addition, the standard deviation and correlation coefficient values of the samples were calculated and discussed. According to the correlation coefficient value, it can be said that there is a positive correlation between metal ion ratios and magnetic susceptibility.

Pathways for the Formation of Formamide, a Prebiotic Biomonomer: Metal-Ions in Interstellar Gas-Phase Chemistry.

The chemistry occurring in the interstellar medium (ISM) is an active area of contemporary research. New aspects of interstellar chemistry are getting unraveled regularly. In this context, the role of metal-ions in the chemistry occurring in the ISM is not well-studied so far. Herein, we highlight the role of metal-ions in interstellar chemistry. For this purpose, we choose the problem of gas-phase formamide formation in interstellar molecular clouds. Formamide is a key biomonomer and contains the simplest peptide [-(C═O)-NH-] linkage. With its two electronegative atoms ("O" and "N"), it provides an excellent platform to probe the role of the metal-ions. The metal-ions chosen are Na+, K+, Al+, Mg+, and Mg2+-all of them present in the ISM. The metal-ions are studied in three different forms as bare positively charged ions, as hydrated metal-ions co-ordinated with a molecule of water, and when the metal-ions are part of a neutral covalent molecule. With the aid of electronic structure calculations [CCSD(T) and DFT methods], we study different gas-phase pathways which result in the generation of interstellar formamide. Throughout our study, we find that metal-ions lower the barriers (with Mg+, Mg++, and Al+ offering maximal stabilization of the transition states) and facilitate the reactions. The chemical factors influencing the reactions, how we consider the putative conditions in the ISM, the astrochemical implications of this study, and its connection with terrestrial prebiotic chemistry and refractory astrochemistry are subsequently presented. Based on our results, we also recommend the detection of two new closed-shell molecules, NH2CH2OH (aminomethanol) and CH2NH2+ (iminium ion), and two open-shell molecules, CONH2 (carbamyl radical) and HCONH (an isomer of carbamyl radical), in the ISM.

ESIPT-based fluorescent probe for bioimaging and identification of group IIIA ions in live cells and zebrafish.

Aluminum (Al), gallium (Ga), indium (In) are three essential elements in group IIIA of the periodic table, which all share similar chemical properties and are also vital in many aspects of bio- and environmental systems. Proper control of their levels is thus necessary as overexposure to them has been linked to onsets of many diseases. Fluorescence based molecular probes have always been the driving horse for detecting vital ions including group IIIA ions. However, only a few such probes have been reported so far and all of them are faced with one or more shortcomings such as not very high sensitivity, incapability to detect multiple ions simultaneously, and poor cell penetration abilities due to emitted fluorescence at shorter wavelengths. To meet those challenges, we herein presented the successful development and application of a novel group IIIA ions fluorescent probe, NBD-hnap, in live RAW264.7 cell and zebrafish models, especially the imaging of ocular tumor cell OCM-1 (human choroid melanoma cells). NBD-hnap was synthesized by a simple conjugation of NBD and hnap molecules under suitable conditions. Subsequent experimental analysis and theoretical calculations confirmed that NBD-hnap forms a 1:1 chelate with each of three selected group IIIA ions. Further evaluation proved that NBD-hnap can realize highly sensitive [LODs of 113, 82 and 150 nM for Al(III), Ga(III), and In(III) respectively in aqueous solutions] and highly selective (over a dozen of interfering cations) through an ESIPT-based fluorescent sensing mechanism with strong far-red emission around 640 nm. Those value merits make NBD-hnap superior to other group IIIA ion probes reported before and NBD-hnap is thus expected to find wider and greater applications in the near future.

Impacts of low salinity exposure and antibiotic application on gut transport activity in the Pacific spiny dogfish, Squalus acanthias suckleyi.

The role of the marine elasmobranch gastrointestinal tract in nitrogen-recycling and osmotic homeostasis has become increasingly apparent, with the gut microbial community likely playing a significant role converting urea, an important osmolyte in elasmobranchs, into ammonia. The Pacific spiny dogfish can experience and tolerate reduced environmental salinities, yet how this environmental challenge may affect the microbiome, and consequently nitrogen transport across the gut, is as of yet unknown. In the present study, excised gut sac preparations were made from dogfish acclimated to the following: full-strength seawater (C), low salinity for 7 days (LS), and after acute transfer of LS-acclimated fish to full-strength SW for 6 h (AT). Significantly reduced microbial derived urease activity was observed in the mucosal saline of gut sac preparations from the LS (by 81%) and AT (by 89%) treatments relative to the C treatment. Microbial derived cellulase activity from mucosal saline samples tended to follow similar patterns. To further ensure an effective decrease in the spiral valve microbial population, an antibiotic cocktail was applied to the mucosal saline used for in vitro measurements of ion, water, and nitrogen flux in these gut sac preparations. This caused a further 57-61% decrease in the mucosal saline urease activity of the C and LS treatments. Overall, we observed relatively little flux across the stomach for all measured parameters aside from water movement, which switched from a net efflux in control fish to a net influx in acutely transferred fish, indicative of drinking. While no significant differences were observed in terms of nitrogen flux (urea or ammonia), we tended to see the accumulation of ammonia in the spiral valve lumen and a switch from efflux to influx of urea in control versus acutely transferred fish. The increased ammonia production likely occurs as a result of heightened metabolism in a challenging environment, while the retention and acquisition of urea is suggestive of nitrogen scavenging under nitrogen-limiting conditions.

Accumulation Pattern of Inorganic Elements in Scaly Tooth Mushroom (Sarcodon imbricatus) from Northern Poland.

Several studies have documented contamination levels and daily intake of metallic elements from foodstuffs including rice, maize, pulses, vegetables, fruits, fish, meat, egg, milk etc., however, limited literature is available on metal contamination levels in wild growing mushrooms and possible human exposure via consumption of it. Sarcodon imbricatus is an edible mushroom, commonly consumed in many parts of the world. Very few studies have been conducted on inorganic elemental composition in fruiting bodies (edible part) of this fungus. In this study, elements such as silver (Ag), aluminum (Al), barium (Ba), calcium (Ca), cadmium (Cd), cobalt (Co,) chromium (Cr), copper (Cu), iron (Fe), mercury (Hg), potassium (K), magnesium (Mg), manganese (Mn), sodium (Na), nickel (Ni), phosphorous (P), lead (Pb), rubidium (Rb), strontium (Sr) and zinc (Zn) were measured in caps and stems of fruiting bodies of S. imbricatus collected from the Wdzydze forests in Central and the Augustowska Primeval forest in Eastern Poland. Results revealed that a wide variation in concentrations of various metals in caps and stems samples collected from the two forests. Toxic metallic elements such as Cd and Hg showed preferential accumulation in caps than stems samples from both the forests. However, the concentrations of Cd, Hg and Pb in the mushroom samples were below the established weekly intake tolerance limits.

Characterisation of gunshot residues from non-toxic ammunition and their persistence on the shooter's hands.

The aim of this work was to characterise three non-toxic ammunition (NTA) from the GECO and Fiocchi brands, which are available in the Italian market. Characterisation was carried out by considering both the elemental chemical composition and morphology, using scanning electron microscopy coupled with energy-dispersive X-ray analysis (SEM-EDS). Particles were collected from both the cartridge cases and the shooters' hands after shooting tests. Six volunteers fired two shots for each ammunition. Several elements, such as aluminium, potassium, silicon, sulphur, titanium and zinc were found in gunshot residue (GSR) particles from different ammunition. We also studied the persistence of these types of GSR on the hands of the shooters in a range between 1 and 6 h after shooting. The GSR particles from the three NTA tested were found on the hands of shooters until 6 h after the shots. The characterisations undertaken in this work will be useful for specialists in forensic science and legal medicine to evaluate trace evidence from these new NTA in casework, as such formulations are in growth.

Association Between Thyroid Hormone Status and Trace Elements in Serum of Patients with Nodular Goiter.

The present study investigated the status of calcium and magnesium as well as essential trace elements including iodine, selenium, copper, iron, and zinc in adults residing in the Zhytomyr region of Ukraine. In addition, the relative risk of goiter occurrence was evaluated. In this comparative study, 40 adults without goiter (control group) and 16 adults with diagnosed nodular goiter (NG) were examined. Inductively coupled plasma optical emission spectrometry (ICP-OES) was used for the measurements of Mg, Ca, Se, Zn, Cu, and Fe in serum of patients with NG and control group. Patients with nodular goiter had lower serum values of Ca, Mg, Se, Cu, Fe, and Zn than those in the control group. The presence of mild iodine deficiency was evident in both groups with the median urinary iodine excretion (UIE) 80.5 µg/L in the control group and 64.5 µg/L in goiter group. There was a positive association between goiter presence and low concentration of Ca in serum (odds ratio (OR) = 2.29 (1.26-3.55), p < 0.05) in the NG group. High relative risk of goiter was observed at low concentrations of magnesium (OR = 3.33 (1.39-7.62), p < 0.05) and selenium (OR = 1.63, (1.16-1.78), p < 0.05) in comparison with OR values in the control group. Low concentrations of Ca, Mg, Zn, and Se in serum combined with reduced UIE resulted in the highest risk of goiter (OR = 12.5, (2.15-79.42), p < 0.01). This study proved that Thyroglobulin concentration in serum is the reliable indicator of nodular goiter. We also suggest that a combination of low concentrations of Ca, Mg, Zn, Cu, and Se in blood serum, and reduced iodine concentration in urine resulted in the highest risk of nodular goiter development.

Application of Group I Metal Adduction to the Separation of Steroids by Traveling Wave Ion Mobility Spectrometry.

Steroids represent an interesting class of small biomolecules due to their use as biomarkers and their status as scheduled drugs. Although the analysis of steroids is complicated by the potential for many isomers, ion mobility spectrometry (IMS) has previously shown promise for the rapid separation of steroid isomers. This work is aimed at the further development of IMS separation for the analysis of steroids. Here, traveling wave ion mobility spectrometry (TWIMS) was applied to the study of group I metal adducted steroids and their corresponding multimers for five sets of isomers. Each set of isomers had a minimum of one dimeric metal ion adduct that exhibited a resolution greater than one (i.e., approaching baseline resolution). Additionally, ion-neutral collision cross sections (CCSs) were measured using polyalanine as a calibrant, which may provide an additional metric contributing to analyte identification. Where possible, measured CCSs were compared to previously reported values. When measuring CCSs of steroid isomers using polyalanine as the calibrant, nitrogen CCS values were within 1.0% error for monomeric sodiated adducts and slightly higher for the dimeric sodiated adducts. Overall, TWIMS was found to successfully separate steroids as dimeric adducts of group I metals. Graphical Abstract ᅟ.

Icariin prevents bone loss by inhibiting bone resorption and stabilizing bone biological apatite in a hindlimb suspension rodent model.

Bone loss induced by microgravity is a substantial barrier to humans in long-term spaceflight. Recent studies have revealed that icariin (ICA) can attenuate osteoporosis in postmenopausal women and ovariectomized rats. However, whether ICA can protect against microgravity-induced bone loss remains unknown. In this study, the effects of ICA on a hindlimb suspension rodent model were investigated. Two-month-old female Wistar rats were hindlimb suspended and treated with ICA (25 mg·kg-1·d-1, i.g.) or a vehicle for 4 weeks (n = 6). The bone mass density of the hindlimbs was analyzed using dual-energy X-ray absorptiometry and micro-CT. mRNA expression of osteogenic genes in the tibia and the content of bone metabolism markers in serum were measured using qRT-PCR and ELISA, respectively. The bone mineral phase was analyzed using X-ray diffraction and atomic spectrometry. The results showed that ICA treatment significantly rescued the hindlimb suspension-induced reduction in bone mineral density, trabecular number and thickness, as well as the increases in trabecular separation and the structure model index. In addition, ICA treatment recovered the decreased bone-related gene expression, including alkaline phosphatase (ALP), bone glaprotein (BGP), and osteoprotegerin/receptor activator of the NF-κB ligand ratio (OPG/RANKL), in the tibia and the decreased bone resorption marker TRACP-5b levels in serum caused by simulated microgravity. Notably, ICA treatment restored the instability of bone biological apatite and the metabolic disorder of bone mineral elicited by simulated microgravity. These results demonstrate that ICA treatment plays osteoprotective roles in bone loss induced by simulated microgravity by inhibiting bone resorption and stabilizing bone biological apatite.

Stability of Major Geogenic Cations in Drinking Water-An Issue of Public Health Importance: A Danish Study, 1980⁻2017.

Concentrations and spatial variations of the four cations Na, K, Mg and Ca are known to some extent for groundwater and to a lesser extent for drinking water. Using Denmark as case, the purpose of this study was to analyze the spatial and temporal variations in the major cations in drinking water. The results will contribute to a better exposure estimation in future studies of the association between cations and diseases. Spatial and temporal variations and the association with aquifer types, were analyzed with spatial scan statistics, linear regression and a multilevel mixed-effects linear regression model. About 65,000 water samples of each cation (1980⁻2017) were included in the study. Results of mean concentrations were 31.4 mg/L, 3.5 mg/L, 12.1 mg/L and 84.5 mg/L for 1980⁻2017 for Na, K, Mg and Ca, respectively. An expected west-east trend in concentrations were confirmed, mainly explained by variations in aquifer types. The trend in concentration was stable for about 31⁻45% of the public water supply areas. It is therefore recommended that the exposure estimate in future health related studies not only be based on a single mean value, but that temporal and spatial variations should also be included.

Metals in Racomitrium lanuginosum from Arctic (SW Spitsbergen, Svalbard archipelago) and alpine (Karkonosze, SW Poland) tundra.

Arctic-alpine tundra habitats are very vulnerable to the input of relatively small amounts of xenobiotics, and thus their level in such areas must be carefully controlled. Therefore, we collected the terrestrial widespread moss Racomitrium lanuginosum (Hedw.) Brid. in Spitsbergen in the Arctic moss lichen tundra and, for comparison, in the Arctic-alpine tundra in the Karkonosze (SW Poland). Concentrations of the elements Cd, Co, Cr, Cu, Fe, Hg, Li, Mn, Mo, Na, Ni, Pb, V, and Zn in this species and in the parent rock material were measured. We tested the following hypothesis: R. lanuginosum from Spitsbergen contains lower metal levels than the species from the Karkonosze collected at altitudes influenced by long-range transport from former Black Triangle industry. Principal component and classification analysis (PCCA) ordination revealed that mosses of Spitsbergen were distinguished by a significantly higher Na concentration of marine spray origin and mosses of Karkonosze were distinguished by significantly higher concentrations of Cd, Cr, Cu, Fe, Hg, Li, Mn, Pb, V, and Zn probably from long-range atmospheric transport. The influence of the polar station with a waste incinerator resulted in significantly higher Co, Li, and Ni concentrations in neighbouring mosses in comparison with this species from other sites. This investigation contributes to the use of R. lanuginosum as a bioindicator for metal contamination in Arctic and alpine tundra regions characterised by severe climate habitats with a restricted number of species. This moss enables the control of pollution usually brought solely by long-range atmospheric transport in high mountains as well as in Arctic areas.

A procedure to evaluate the factors determining the elemental composition of PM2.5. Case study: the Veneto region (northeastern Italy).

The Po Valley is one of the most important hot spots in Europe for air pollution. Morphological features and anthropogenic pressures lead to frequent breaching of air quality standards and to high-pollution episodes in an ~46 × 103-km2-wide alluvial lowland. Therefore, it is increasingly important to study the air quality in a wide geographical scale to better implement possible and successful mitigation measures. The Veneto region lies in the eastern part of the Po Valley and the elemental composition of PM has been mainly studied in the Venice area, whereas scarce data are available for the remaining territory of the region. In this study, the elemental composition of PM2.5 was investigated over 1 year (2012-2013) at six major cities of the Veneto region. Samples were analyzed for 16 elements (Ca, Al, Fe, S, K, Mg, Ti, Mn, Zn, Ba, As, Ni, Pb, Sb, V, and Cu), and results were processed to investigate spatial and seasonal variations, the influence of meteorological factors, and the most probable sources by using a procedure based on (i) elemental ratios (Cu/Sb, Cu/Zn, Cu/Pb, Mn/V, V/Ni, and Zn/Pb), (ii) cluster analysis on wind data, and (iii) conditional probability function (CPF). The percentage of elements in PM2.5 ranged between 11 and 20%, and Ca and S were the most abundant elements in the region. Typical seasonal variations and similar trends were exhibited by each element, especially in the lowland. Some elements such as Zn, K, Mn, Pb, and Sb were found at high concentrations during the cold period. However, no similar dispersion processes were observed throughout the region, and their concentrations were mostly depending on individual local sources. In the alpine and foothill parts of the region, lower concentrations were recorded with respect to the Po Valley cities, which resulted enriched of most of the elements considered in this study. The cluster analysis on wind data and the CPF of the ratio-related sources demonstrated that a widespread pollution condition exists in the region, apart from the coastal area. However, specific directions (e.g., a link with high-traffic roads, industrial areas, and airports) resulted the most probable explanation for each ratio-related source. In addition, the Veneto region hosts one of the most important Mediterranean ports for the cruise sector (Venice harbor), and its impact was previously demonstrated in the historical city center. In this study, the impact of Venice shipping emissions was estimated to be 3.5% of PM2.5 in some particular days.

MetalPDB in 2018: a database of metal sites in biological macromolecular structures.

MetalPDB (http://metalweb.cerm.unifi.it/) is a database providing information on metal-binding sites detected in the three-dimensional (3D) structures of biological macromolecules. MetalPDB represents such sites as 3D templates, called Minimal Functional Sites (MFSs), which describe the local environment around the metal(s) independently of the larger context of the macromolecular structure. The 2018 update of MetalPDB includes new contents and tools. A major extension is the inclusion of proteins whose structures do not contain metal ions although their sequences potentially contain a known MFS. In addition, MetalPDB now provides extensive statistical analyses addressing several aspects of general metal usage within the PDB, across protein families and in catalysis. Users can also query MetalPDB to extract statistical information on structural aspects associated with individual metals, such as preferred coordination geometries or aminoacidic environment. A further major improvement is the functional annotation of MFSs; the annotation is manually performed via a password-protected annotator interface. At present, ∼50% of all MFSs have such a functional annotation. Other noteworthy improvements are bulk query functionality, through the upload of a list of PDB identifiers, and ftp access to MetalPDB contents, allowing users to carry out in-depth analyses on their own computational infrastructure.

Physicochemical and biochemical parameters in milk of Serbian breastfeeding women.

BACKGROUND/AIM: This study was undertaken to determine the changes and relationships between some important milk constituents as well as physical, rheological, and biochemical parameters of milk obtained from Serbian breastfeeding mothers. MATERIALS AND METHODS: Physicochemical and biochemical parameters and the concentrations of vitamins, uric acid, and minerals were determined during the three periods of lactation covering colostrum, transitional, and mature milk collected from 67 mothers who had a term-pregnancy. RESULTS: Large interindividual variations regarding many parameters were found between mothers at the same period of lactation, but the average values were mostly in the expected and recommended ranges. For some parameters, our values are quite different in relation to the milk of women from other countries or data reported by other authors. CONCLUSION: Differences in vitamin and mineral contents and physicochemical and rheological characteristics of milk obtained by Serbian breastfeeding mothers compared to that of mothers from other parts of the world have been found. This paper presents the measured data of some physical parameters of human milk about which there is little information in the literature.

Influence of Monovalent Cation Size on Nanodomain Formation in Anionic-Zwitterionic Mixed Bilayers.

Phosphatidylserine (PS) and phosphatidylcholine (PC) are two of the major anionic and zwitterionic phospholipids in mammalian cell membranes. Ion-PS interaction is hypothesized to play a crucial role in a range of biological events including membrane fusion, lipid phase modulation, membrane protein insertion and translocation. In this study, we characterize lipid nanodomain formation in PC/PS mixed bilayers using coarse-grained simulations. We investigate the role of monovalent cation sizes in modulating lipid-ion binding modes and lipid demixing. Our simulations suggest that certain lipid-ion binding modes lead to growth of ion-mediated PS lipid clusters. The existing literature reveals the polymorphism in binding and partitioning patterns in monovalent cations (Na+, K+, and Li+) with anionic lipids. Our work provides a microscopic view on the ion-size-dependent PS lipid packing pattern observed experimentally. A coupled relationship between lipid curvature and asymmetry is observed in highly demixed PC/PS mixed bilayers.

Comprehensive assessment of seldom monitored trace elements pollution in the riparian soils of the Miyun Reservoir, China.

The South-to-North Water Diversion Project has aroused widespread concerns about the potential ecological risks posed by the project, especially for the Miyun Reservoir (MYR). The potential release risk of metals from the flooded riparian soils into MYR after water impoundment is one of key scientific problems. In this study, riparian soil samples were collected considering three vertical heights (130, 140, and 145 m) and four types of land uses in the MYR areas, namely, forestland, grassland, wasteland, and recreational land. We analyzed soils texture, the content and chemical fractionations of seldom monitored trace elements (SMTEs): Li, Be, B, V, Co, Ni, Ga, Sn, Sb, Tl, and Bi). Results showed that the four types of soils in MYR had the similar textures, while recreational land showed significantly higher contents of Ni and V. Additionally, there were no significant differences found for most SMTEs (except for V) at different vertical heights in each soil type, while the concentrations of V at 140 and 145 m in forestland and recreational land were significantly higher than those at 130 m. However, a comprehensive evaluation of potential ecological risk (contamination factor (CF), modified degree of contamination (mCd), and geoaccumulation factor (I geo)) consistently indicated the insignificant contaminations of all SMTEs in MYR soils before water impoundment. The Community Bureau of Reference (BCR) sequential extraction results showed that the chemical fractionations of SMTEs were independent of land use patterns and vertical heights. Co in reducible fractions and Ni were identified as the candidates which had potential to release into MYR when the lands were submerged. Principal component analysis (PCA) and cluster analysis (CA) results suggested that a portion of V, Co, and Ni may originate from anthropogenic activities, and the coal combustion was possibly the main anthropogenic source. The findings of this work would provide valuable information on the environment management of MYR and offer a reference for the investigation on the effect of water impoundment on potential release risk of SMTEs in MYR.

From Widely Accepted Concepts in Coordination Chemistry to Inverted Ligand Fields.

We begin with a brief historical review of the development of our understanding of the normal ordering of nd orbitals of a transition metal interacting with ligands, the most common cases being three below two in an octahedral environment, two below three in tetrahedral coordination, and four below one in a square-planar environment. From the molecular orbital construction of these ligand field splittings evolves a strategy for inverting the normal order: the obvious way to achieve this is to raise the ligand levels above the metal d's; that is, make the ligands better Lewis bases. However, things are not so simple, for such metal/ligand level placement may lead to redox processes. For 18-electron octahedral complexes one can create the inverted situation, but it manifests itself in the makeup of valence orbitals (are they mainly on metal or ligands?) rather than energy. One can also see the effect, in small ways, in tetrahedral Zn(II) complexes. We construct several examples of inverted ligand field systems with a hypothetical but not unrealistic AlCH3 ligand and sketch the consequences of inversion on reactivity. Special attention is paid to the square-planar case, exemplified by [Cu(CF3)4](-), in which Snyder had the foresight to see a case of an inverted field, with the empty valence orbital being primarily ligand centered, the dx2-y2 orbital heavily occupied, in what would normally be called a Cu(III) complex. For [Cu(CF3)4](-) we provide theoretical evidence from electron distributions, geometry of the ligands, thermochemistry of molecule formation, and the energetics of abstraction of a CF3 ligand by a base, all consistent with oxidation of the ligands in this molecule. In [Cu(CF3)4](-), and perhaps more complexes on the right side of the transition series than one has imagined, some ligands are σ-noninnocent. Exploration of inverted ligand fields helps us see the continuous, borderless transition from transition metal to main group bonding. We also give voice to a friendly disagreement on oxidation states in these remarkable molecules.