Miocene echinoids from the Sadat area,south Gebel Ataqa,NW Gulf of Suez,Egypt: systematics,palaeobiogeography

The echinoid fauna from the Miocene sedimentary succession cropping out south Wadi Tweirig, and Wadi Hommath, south Gebel Ataqa, NW Gulf of Suez, has been examined with the aim to known their stratigraphic and paleogeographic distribution. The Miocene succession includes two formations: Sadat Formation, unconformably overlying the middle/upper Eocene rocks at the base and Hommath Formation at the top. Twenty-eight echinoid species (8 regular and 20 irregular) belonging to 18 genera, 13 families, and 7 orders have been identified, systematically described, and illustrated in this work. Eleven species are recorded for the first time from Egypt: ten of these came from the Hommath Formation (Schizechinus cf. serresii Desor (1856), Schizechinus pentagonus Kier 1972, Clypeaster cf. martini des Moulins 1837, Scutella checchiae occidentalis Desio 1934, Scutella melitensis Airaghi 1902, Echinodiscus desori Duncan and Sladen 1883, Echinolampas cf. zeitensis Fourtau 1920, Schizaster lovisatoi Cotteau 1895, Agassizia (Agassizia) powersi Kier 1972, and Hemipatagus ocellatus Defrance (1827)), and one from the Sadat Formation (Clypeaster campanulatus Schlotheim (1820)). The identified fauna shows a strong affinity with the Mediterranean bio-province.     

Microbiostratigraphy of the Upper Paleocene to Middle Eocene Jahrum Formation in the Folded Zagros Zone,SW Iran

The Jahrum Formation (Upper Paleocene to Middle Eocene) is composed of carbonate and dolomitic carbonate rocks in the Zagros Basin. The Zagros is located at the boundary between the Arabian and Eurasian lithosphere plates and represent the orogenic response to a collision between Eurasia and advancing Arabia during the Cenozoic. The study area is located in the northern part of Kuh-E-Tudej, ~175 km southeast of Shiraz in the Folded Zagros Zone. The Jahrum Formation at Kuh-E-Tudej, with a thickness of 190 m, consists of medium to massive bedded limestone. The following foraminiferal index species are identified in the studied section: Fallotella alavensis, Kathina sp., Miscellanea sp., Lockhartia sp.,Orbitolites shirazeinsis, Nummulites sp., Opertorbitolites sp., Dictyoconus cf. egyptiensis, Orbitolites cf. complanatus, Dictyoconus sp., Coskinolina sp., Somalina stefaninii, Discocyclina sp., Praerhapydionina sp., Coskinolina cf. liburnica, Nummulites cf. globulus, Nummulites cf. aturicus, and Alveolina sp. The age of the studied sediments ranges from Upper Paleocene to Middle Eocene. The microbiostratigraphic studies revealed four biozones based on the foraminifers identified in the studied section.     

Permian Calcareous algae from the Khachik Formation at the Ali Bashi Mountains,NW of Iran

Micropaleontological investigations on Permian successions in the NW of Iran based on algae led to the determination of taxa belonging to some families such as Ungdarellaceae (Ungdarella uralica), Gymnocodiaceae (Gymnocodium bellerophontis and Permocalculus sp.), Dasycladales (Mizzia cf. M. yabei), and some microproblematics (Vermiporella nipponica and Pseudovermiporella sodalica). These investigations are mainly focused on the Khachik Formation at the Ali Bashi Mountains. According to the algal community, a lagoon environment is offered for the studied successions.     

The Bajocian–Bathonian plant fossil from the Hojedk formation,Lenjan section,Kerman, Iran

The Jurassic successions represent a wide distribution in North of the Kerman province. These successions include Ab-Haji, Badamu, and Hojedk formations. The Hojedk Formation contains the plant fossils. The Lenjan section is one of the suitable areas for paleontological studies on the Hojedk Formation. The study section is mostly composed of green sandstone and shale with several interbedded coal veins with different thicknesses. The thickness of the Hojedk Formation is about 200 m in the Lenjan section. In this study, seven genera and 13 species of macro plant fossils were identified and described, including Nilssonia undulata, Nilssonia bozorga, Nilssonia berriesi, Nilssonia sp., Klukia cf. exilis, Klukia exilis, Cladophlebis antarctica, Coniopteris lobata, Coniopteris murrayana, Elatocladus confertus, Podozamites sp., Equisetites sp., and Coniopteris sp. The Bajocian–Bathonian can be attributed to the Lenjan section based on the recognized flora.     

The age of the Nodular Limestone Formation (Late Cretaceous), Narmada Basin,central India

The age of the marine Nodular Limestone Formation of the Bagh Group is refined at Substage level through ammonoid and inoceramid index taxa. The study is based on the fresh collections from three well-defined successive intervals (Lower Karondia, Upper Karondia and Chirakhan members) of this formation having excellent exposures in different localities of the Narmada Basin, central India. The first record of the widely distributed Turonian ammonoid genera Spathites Kummel and Decker and Collignoniceras Breistroffer from the Nodular Limestone Formation constrained its age exclusively to Turonian. The Early Turonian species Spathites (Jeanrogericeras) aff. revelieranus (Courtiller) and Mytiloides labiatus (Sclotheim) occur in the lower part, while the Middle Turonian marker Collignoniceras cf. carolinum (d’Obrbigny) and Inoceramus hobetsensis (Nagao and Matsumoto) occurs in the upper part of the Karondia Member. The record of the index species Inoceramus teshioensis (Nagao and Matsumoto) in association with Placenticeras mintoi Vredenburg from Chirakhan Member allows a definite Late Turonian age. The present contribution is an attempt to resolve the controversies in the age of the Nodular Limestone Formation and also demarcation of the three divisions (Early, Middle and Late) of the Turonian Stage in the Narmada Basin, central India.     

Permian macro- and miofloral diversity,palynodating and palaeoclimate implications deduced from the coal-bearing sequences of Singrauli coalfield,Son–Mahanadi Basin,central India

The coal-bearing sequences of Barakar and Raniganj formations exposed in Bina and Jhingurdah open-cast collieries, respectively, are analysed for their macro- and miofloral content. The sediment successions primarily comprise of sandstones, shales, claystones and coal seams. In addition to the diverse glossopterid assemblage, four palynoassemblage zones, namely Zones I and II in Bina Colliery and Zones III and IV in Jhingurdah Colliery, have also been recorded in the present study. The megafossil assemblage from the Barakar strata of Bina Colliery comprises of three genera, namely Gangamopteris, Glossopteris and cf. Noeggerathiopsis. Palynoassemblage-I is characterised by the dominance of non-striate bisaccate pollen genus Scheuringipollenites and subdominance of striate bisaccate Faunipollenites and infers these strata to be of Early Permian (Artinskian) age (Lower Barakar Formation). The palynoassemblage has also yielded a large number of naked fossil spore tetrads, which is the first record of spore tetrads from any Artinskian strata in the world and has a significant bearing on the climatic conditions. The palynoassemblage-II is characterised with the dominance of Faunipollenites over Scheuringipollenites and is indicative of Kungurian age (Upper Barakar Formation). The megafossil assemblage from the Raniganj Formation of Jhingurdah Colliery comprises of five genera with 26 species representing four orders, viz., Equisetales, Cordaitales, Cycadales and Glossopteridales. The order Glossopteridales is highly diversified with 23 taxa and the genus Glossopteris, with 22 species, dominates the flora. The mioflora of this colliery is represented by two distinct palynoassemblages. The palynoassemblage-III is correlatable with the palynoflora of Early Permian (Artinskian) Lower Barakar Formation. The assemblage suggests the continuity of older biozones into the younger ones. The palynoassemblage-IV equates the beds with composition V: Striatopodocarpites–Faunipollenites–Gondisporites assemblage zone of Tiwari and Tripathi (1992) of Late Permian (Lopingian) Raniganj Formation in Damodar Basin. The FAD’s of Alisporites, Klausipollenites, Falcisporites, Arcuatipollenites pellucidus and Playfordiaspora cancellosa palynotaxa in this assemblage enhance the end Permian level of the Jhingurdah Top seam, as these elements are the key species to mark the transition of Permian into the Lower Triassic.     

Campanian-Lower Paleogene gastropods from the Kharga Oasis,south Western Desert,Egypt

The Campanian-Lower Paleogene successions exposed at the Kharga Oasis contain well-preserved gastropods. Nineteen gastropod species are identified and described in detail. Two new species are established: Gisortia khargaensis from the lower Eocene El Rufuf Formation and Ornopsis? barisensis from the lower Paleocene Kurkur Formation. In addition to, Turritella (Torquesia) derbesi Coquand is recorded herein for the first time from Egypt. The studied gastropods belonging to four clades: Sorbeoconcha (Metacerithium abictiforme (Wanner), Mesalia hofana Mayer-Eymar, Mesalia sp., Turritella (Torquesia) derbesi Coquand, Turritella (Torquesia) forgemoli Coquand, Turritella kaserensis Hewaidy and Azab, Turritella sp.), Littorinimorpha (Cypraedia bullina Oppenheim, Gisortia khargaensis nov. sp., Natica farafrensis Wanner, Aporrhais schweinfurthi (Quaas), Drepanocheilus bicarinatus Abbass, Drepanocheilus? sp., Anchura? unicarinatus (Abbass), Epitonium sp.), Neogastropoda (Ornopsis? barisensis nov. sp., Rostellana daniensis (Quaas), Vouta sp.), and Heterobranchia (Avellana cretacea Quaas).     

Bioerosion and encrustation rates in recent mollusk death assemblages on a supratidal siliciclastic setting,Playa Norte,Veracruz State,Mexico

This study presents both qualitative and quantitative data regarding marine mollusk (gastropods and bivalves) shell bioerosion and encrustation based on death assemblages obtained from a recent supratidal environment in Playa Norte, Veracruz State. The objectives of this study were to assess the nature of bioerosion and encrustation processes and to investigate the role of these taphonomic features contributing to the deterioration of natural shell accumulations within a tropical siliciclastic tidal environment. The assemblage comprises 31 species: 13 gastropods and 18 bivalves. The bioerosion and encrustation degrees were low to moderate for both types. The most abundant traces were predatory gastropod structures (Oichnus paraboloides and O. simplex), whereas sponge borings (Entobia isp.), polychaete dwellings (Caulostrepsis taeniola), and echinoid raspings (Gnatichnus isp.) were less frequent. The encrusting organisms include polychaete serpulids, bryozoans, and rare foraminifers (Homotrema rubrum). Because of the low bioerosion and encrustation degrees occurring in this area, accumulation is expected to predominate over biotic destruction. As deposition conditions (richly fossiliferous carbonate sandstone beds) were similar to those prevailing in the Tuxpan Formation during the Miocene (Langhian), it is suggested that this study provides an equivalent reference to interpret mollusk fossil assemblages located in this site.     

Age and palynological characteristic of the Dongning Formation (Eastern Heilongjiang,China)

The taxonomic composition of the palynological assemblage of the Dongning Formation is supplemented. The palynological assemblage corresponds to those from the Lipovtsy Formation (Aptian) in the Razdolnaya Basin of Primorye (Russia) and the Muling Formation (Aptian) in the Jixi Basin of eastern Heilongjiang (China). It is found that the age of the Dongning Formation is Aptian. The palynological assemblage is characterized by dominance of spores of Gleicheniaceae; they are accompanied by spores of Cyatheaceae. The most important feature of the palynological assemblage of the Dongning Formation is the presence of angiosperm pollen (Tricolpites sp., T. micromunus, T. vulgaris, Retitricolpites georgiensis, R. vulgaris, Clavatipollenites hughesii, Quercites sparsus, Fraxiniopollenites variabilis).     

Potency of constructed wetlands for deportation of pathogens index from rural,urban and industrial wastewater

Pathogen removal is essential for wastewater treatment and its potential reuse in agriculture. Three field-scale wastewater treatment systems consisting of free surface flow were operated around 1.5 years receiving water from urban domestic, rural domestic and industrial sources. The study was conducted to evaluate seasonal performance of constructed wetland systems in removing Escherichia coli, Enterococci and total coliforms under continuous hydraulic flow. Results displayed that all three wetlands gain recognition in removing pathogen load with high removal efficacy till water reaches output ports. Removal efficiencies were even higher, 66–93, 78–92 and 80–94% for E. coli, Enterococci and total coliforms, respectively, within constructed wetlands. Remarkably at shorter temporal scales in CW-A, greater homogeneity of pathogen concentrations was assessed at wetland outlet sites. In outlet ports, results displayed a highly effective removal of E. coli concentration 80–90% (June 2015), 86–92% (October 2015) and 79–92% (February 2016), Enterococci 80–94% (June 2015), 83–94% (October 2015) and 80–94% (February 2016) and total coliforms 85–93% (June 2015), 87–95% (October 2015) and 88–96% (February 2016). Positive correlation was observed between bacterial indicators (E. coli–Enterococci, r = 0.038; p < 0.01 and E. coli–total coliforms, r = 0.142; p < 0.01). Removal of bacterial indicators in constructed wetland was also displayed by PCA in which three-component analysis of variance was 98.39% and showed a clear decrease in measured parameter gradients toward samples from outlet ports. Constructed wetlands provide cost-effective treatment systems for reducing the pathogen load in wastewater in variable agro-climatic conditions and thus improve water quality.     

The Influence of Oyster Farming on Sediment Bacterial Communities

Aquaculture currently provides half of all fish for human consumption, and this proportion is expected to increase to meet the growing global demand for protein. As aquaculture, including oyster farming, expands, it is increasingly important to understand effects on coastal ecosystems. The broad-scale ecological effects of oyster aquaculture are well documented; however, less is known regarding the influence of oyster aquaculture on sediment bacterial communities. To better understand this relationship, we compared three different oyster farming practices that varied in oyster biomass and proximity of oysters to the sediment. We used high-throughput sequencing and quantitative polymerase chain reaction to examine the effect of oyster farming on sediment bacterial communities. We examined the entire bacterial community and looked specifically at bacteria that support essential estuarine ecosystem services (denitrifiers), as well as bacteria that can be detrimental to human health (members of the Vibrio genus). We found that oyster biomass increased Vibrio richness and sediment carbon content, which influenced bacterial community composition. When compared to reference sites, the overall abundance of bacteria was increased by the bottom planting method, but the associated increases in denitrifiers and Vibrio were not significant. We were unable to detect V. parahaemolyticus, V. vulnificus, or V. cholera, the three most common Vibrio pathogens, in any sample, suggesting that oyster farming did not enhance these potential human pathogens in sediments at the time of sampling. These results highlight how differences in oyster farming practice can affect sediment bacterial communities, and the ecosystem services they provide.     

Crystal chemistry of tremolite–tschermakite solid solutions

Tremolite–tschermakite solid solutions have been synthesized between 700 and 850 °C and 200 and 2000 MPa. The starting materials were oxide–hydroxide mixtures and an additional 0.1–1.8 molal CaBr₂ solution. The run products were characterized using SEM, HRTEM, EMP, XRD and FTIR. The synthesized Al tremolites formed needles and lath-shaped crystals of up to 300 × 20 μm. HRTEM investigations showed that the majority of the amphiboles were well ordered. The EMP analysis revealed that the Al tremolites were solid solutions in the ternary tremolite–tschermakite–cummingtonite. The highest observed Al content was close to the composition of magnesiohornblende (X_ts=0.54). Different cummingtonite concentrations (X_cum=0.00–0.18) were observed, which generally increased with Al content. Rietveld refinements of the lattice constants showed a linear decrease of the cell parameters a and b with increasing Al content, whereas c and β increased. Small deviations from the linear behaviour were caused by variable amounts of the cummingtonite component. For pure tschermakite lattice parameters of a=9.7438(11) Å, b=17.936(14) Å, c=5.2995(3) Å, β=105.68(9)° and V=891.7 ± 1.4 ų were extrapolated by least-squares regression. Using the a and β lattice parameters for tremolite, tschermakite and cummingtonite, it was possible to derive amphibole compositions using powder XRD. IR spectra of the Al tremolites showed a total of 12 individual bands. The FWHMs of all bands increased with increasing Al content. According to their FWHMs, these bands were grouped into three band systems at 3664–3676 cm^?1 (I), 3633–3664 cm^?1 (II) and 3526–3633 cm^?1 (III). Assuming ^[6]Al substitution at M2 and/or M3 and ^[4]Al at T1, three principal different configurational groups could be assigned as local environments for the proton. I: only Si⁴⁺ at T1 and one or two Al³⁺ at M2 and/or M3_far, II: one Al³⁺ at T1 and one to three Al³⁺ at M2 and/or at M3_far, III: either Al³⁺ on M3_near and/or two Al³⁺ on T1 and additional one to four Al³⁺ at M2. It is assumed that these three configurational groups correspond to the three groups of observed bands. This was quantitativly supported by Monte-Carlo simulations. A model with random distribution at M2 and M3 including Al avoidance at tetrahedral and octahedral sites yielded the best agreement with the spectroscopical results.     

Early Triassic palynomorphs from Kuraloi Block,Belphar area,Ib-River coalfield,Mahanadi basin,Odisha

A rich assemblage of palynomorphs including miospores and megaspores has been recorded from the bore core no. IBKAN-2 drilled at a depth of 17.80m in Kuraloi Block-A, south-west part of the Ib-River Coalfield, Jharsuguda district, Odisha. The miofloral assemblage recovered shows prominence of cingulate, zonate, taeniate, non-striate and non saccate palynotaxa which indicate an early Triassic age and is comparable with the palynoassemblages of the same age known from the Damodar basin, India. The megaspore assemblage includes eight genera and fifteen species namely, Banksisporites karanpuraensis, B. indicus, B. utkalensis, Banksisporites sp., Barakarella pantii, Barakarella sp., Biharisporites spinosus, Biharisporites sp., Erlansonisporites triassicus, Erlansonisporites cf. erlansonii, Erlansonisporites sp. Jhariatriletes sp., Singhisporites sp., Ramispinatispora sp. and Talchirella trivedii. Records of megaspores are sparse in the early Triassic of Gondwana basins of India. The present study records the first occurrence of miospores and megaspores from the early Triassic of Mahanadi basin besides substantiating the earlier data.     

Seismic attenuation in Jati area,Lower Indus Basin,Pakistan

Reduced amplitude and distorted dispersion of seismic waves caused by attenuation, especially strong attenuation, always degrade the resolution of migrated images. To improve seismic imaging, attenuation must be compensated. This study addresses the factors causing seismic attenuation in Jati Block. Jati Block lies in Lower Indus Basin, Pakistan, approximately 25 mi north of the offshore Indus. Method used for Q factor is empirical equation method. Q factor correlation indicates that there are three major zones of attenuation in Jati block, i.e., zone I (surface to top Khadro), zone II (Upper Goru Formation), and zone III (Lower Goru Formation). Lowest Q value is in zone I, followed by zone II and zone III, respectively. Commonly, Khadro Formation (Basalt) of Paleocene and saucer-shaped igneous intrusion is considered as sources of attenuation. However, surprisingly, Khadro Formation of Paleocene and saucer-shaped igneous intrusion is zone of minimum attenuation and causes minimal transmission loss. Anisotropy analysis is performed to determine cause of attenuation within these zones. Thomson anisotropic parameters are computed for vertical wells using Backus averaging algorithm. These parameters are calibrated using sonic scanner data available for one well. Correlation of Q factor curve with mud log suggests that loose, unconsolidated sands and sand-shale layering are sources of attenuation within zone I. Attenuation in this zone is mostly due to fluid motion relative to the framework of loosely packed grains. Major lithology of Upper Goru Formation is marl. It is a slow formation, and in this formation, P wave loses energy to the formation in what is known as leaky P mode (sonic logging) and is dispersive (seismic). Epsilon (?) value is greater than almost 0.02 throughout Lower Goru Formations, indicating that this formation is strongly anisotropic. Fluctuation of epsilon (?) in Lower Goru Formation also suggests that this formation is causing layer-induced anisotropy. This layer-induced anisotropy in Lower Goru Formation added by dispersive and slow nature of Upper Goru Formation causes rapid attenuation.     

Differences in the Soluble,Residual Phosphate Concentrations at Which Coastal Phytoplankton Species Up-regulate Alkaline-Phosphatase Expression,as Measured By Flow-Cytometric Detection of ELF-97® Fluorescence

The enzyme-labeled fluorescence (ELF-97®) substrate produces an insoluble, fluorescent yellow-green product at the site of alkaline-phosphatase (AP) activity. Fifteen coastal phytoplankton species were tested to determine if AP activity could be detected in phosphate-depleted media. All species tested, except Synechococcus bacillaris, expressed AP activity. Subsequently, threshold concentrations of soluble reactive phosphate (SRP) at which AP activity could be detected by ELF-97® were determined for Chaetoceros neogracile, Chlorella autotrophica, Isochrysis sp., Prorocentrum minimum, and Tetraselmis chui. Microalgal species differed significantly in the SRP concentration at which AP activity was first detectable (10.1–16.4 µM), well above concentrations normally considered limiting for phytoplankton. P. minimum began to express AP activity at a higher SRP concentration than the other algal species; this may be attributable to a relatively high DNA/cell ratio in P. minimum, compared to the other phytoplankton. Thus, phytoplankton species may respond to phosphorus deficiency at high SRP concentrations.     

Separate and Combined Effects of Estuarine Stress Gradients and Disturbance on Oyster Population Development on Restored Reefs

Disturbance combined with the effects of multiple stress gradients can produce biotic outcomes that are complex and perhaps not predictable based on knowledge of the individual stress variables. We analyzed oyster (Crassostrea virginica) colonization of novel substrate via structural equation modeling (SEM) to test cause-and-effect multivariate models posed a priori as hypotheses. We separately analyzed long-term data on water quality (WQ), canal flow, and rainfall to determine drivers of chlorophyll a for use in the oyster SEM. The best oyster SEM for adult (R ² = 0.74) and small <20-mm (R ² = 0.48) oyster abundances combined WQ stress gradients produced by normal canal flow with disturbance caused by extremely high flow. There was a ?0.26 direct negative effect of increasing salinity during normal canal flow on the small oyster size class possibly reflecting undocumented increases in marine predators and a negative total effect (negative indirect + direct effects) of the salinity gradient on adult oysters. Very low salinity occurring during extreme (disturbance) canal flows produced large negative direct and total effects on small oysters, but no significant total effect for adult oysters. Chlorophyll a (Chl-a) during normal canal flow had negative total effects on small oysters but positive total effects on adult oysters. The effect of max Chl-a on adult oysters was strongly negative during disturbance-level canal flow. Turbidity during normal canal flow had no effect on small or adult oysters. However, during disturbance flows, the maximum turbidity had strong negative effects. Stress and disturbance from freshwater releases impacted oyster recruitment and survival, affecting the colonization and growth of oysters.     

Plug shaped burrows <Emphasis Type="Italic">Conichnus - Conostichus</Emphasis> from the Late Cretaceous of Bagh Group,Gujarat, western India

Plug-shaped ichnofossils Conichnus conicus, Conostichus broadheadi and C. stouti are found in the intercalated micritic sandstone and sandy allochemic limestone shale sequence of Bagh Group, Narmada district, Gujarat. These ichnospecies occur at two stratigraphic levels and shows distinct morphological features interpreted as resting/dwelling structures of sea anemone. The occurrence of these ichnospecies along with oyster fossils genera like Bosostrea and Indostrea indicate shallow marine environment.     

Early Cretaceous <Emphasis Type="Italic">Neotrocholina</Emphasis> Reichel, 1956 from the Tirgan Formation,Kopet Dagh sedimentary basin,NE Iran: systematic and biometric interpretation

Neotrocholina Reichel, 1956 is one of the most important benthic foraminifera in Early Cretaceous. Some of the species of this genus are indexes in biostratigraphy especially for this interval (e.g., Neotrocholina friburgensis: Late Barremian–Early Aptian; Neotrocholina aptiensis: Early Aptian). In order to conduct accurate paleontological investigations, sampling from the carbonate units of the Tirgan Formation in Kopet Dagh sedimentary basin is done. According to the occurrence level in the studied stratigraphic sections as well as biometric interpretations, two species of this genus (N. friburgensis and Neotrocholina valdensis) are pointed out.     

Assessment of potential sediment contamination using screening methods (XRF,TGA/MS) taking into account principles of green chemistry,Eastern Slovakia

Mining and milling of metal ores coupled with industries have bequeathed many countries the legacy of wide distribution of metal contaminants in sediments. The aim of this study was to assess potential sediment contamination via useful screening methods (XRF, CHNS, TGA/MS). The sediments were collected from the water reservoir Krompachy Eastern Slovakia in April 2015. Within the frame of evaluation it was found that the concentrations of the study elements (Cu, Zn, As, Pb, Cr, Ni, Cd) exceeded some of the MPC, TV and IV values. Sample c was the most polluted by metals, which evident according to it’s the highest CHNS proportion as well as the highest clay and silt proportion. In the samples studied the best correlation was confirmed between weight losses in the temperature range (400–620 °C) and the following metal concentrations: Cu (r = 0.89), Zn (r = 0.88), As (r = 0.93), Hg (r = 0.83), Pb (r = 0.87). The greatest proportions of m/z 44, m/z 18 were detected at temperatures (400–620 °C) associated with decomposition of minerals such as siderite, barite, and exothermic loss of more refractory aromatic C took also place.     

Probing the local environment of substitutional Al$$^{}$$ in goethite using X-ray absorption spectroscopy and first-principles calculations

We present experimental and calculated Al K-edge X-ray absorption near-edge structure (XANES) spectra of aluminous goethite with 10–33 mol% of AlOOH and diaspore. Significant changes are observed experimentally in the near- and pre-edge regions with increasing Al concentration in goethite. First-principles calculations based on density functional theory (DFT) reproduce successfully the experimental trends. This permits to identify the electronic and structural parameters controlling the spectral features and to improve our knowledge of the local environment of \(\hbox {Al}^{3+}\) in the goethite–diaspore partial solid solution. In the near-edge region, the larger peak spacing in diaspore compared to Al-bearing goethite is related to the nature (Fe or Al) of the first cation neighbours around the absorbing Al atom (Al*). The intensity ratio of the two near-edge peaks, which decreases with Al concentration, is correlated with the average distance of the first cations around Al* and the distortion of the \(\hbox {AlO}_6\) octahedron. Finally, the decrease in intensity of the pre-edge features with increasing Al concentration is due to the smaller number of Fe atoms in the local environment of Al since Al atoms tend to cluster. In addition, it is found that the pre-edge features of the Al K-edge XANES spectra enable to probe indirectly empty 3d states of Fe. Energetic, structural and spectroscopic results suggest that for Al concentrations around 10 mol%, Al atoms can be considered as isolated, whereas above 25 mol%, Al clusters are more likely to occur.