The evolution of the marine carbonate factory.

Calcium carbonate formation is the primary pathway by which carbon is returned from the ocean-atmosphere system to the solid Earth1,2. The removal of dissolved inorganic carbon from seawater by precipitation of carbonate minerals-the marine carbonate factory-plays a critical role in shaping marine biogeochemical cycling1,2. A paucity of empirical constraints has led to widely divergent views on how the marine carbonate factory has changed over time3-5. Here we use geochemical insights from stable strontium isotopes to provide a new perspective on the evolution of the marine carbonate factory and carbonate mineral saturation states. Although the production of carbonates in the surface ocean and in shallow seafloor settings have been widely considered the predominant carbonate sinks for most of the history of the Earth6, we propose that alternative processes-such as porewater production of authigenic carbonates-may have represented a major carbonate sink throughout the Precambrian. Our results also suggest that the rise of the skeletal carbonate factory decreased seawater carbonate saturation states.

Innovative Homo sapiens behaviours 105,000 years ago in a wetter Kalahari.

The archaeological record of Africa provides the earliest evidence for the emergence of the complex symbolic and technological behaviours that characterize Homo sapiens1-7. The coastal setting of many archaeological sites of the Late Pleistocene epoch, and the abundant shellfish remains recovered from them, has led to a dominant narrative in which modern human origins in southern Africa are intrinsically tied to the coast and marine resources8-12, and behavioural innovations in the interior lag behind. However, stratified Late Pleistocene sites with good preservation and robust chronologies are rare in the interior of southern Africa, and the coastal hypothesis therefore remains untested. Here we show that early human innovations that are similar to those dated to around 105 thousand years ago (ka) in coastal southern Africa existed at around the same time among humans who lived over 600 km inland. We report evidence for the intentional collection of non-utilitarian objects (calcite crystals) and ostrich eggshell from excavations of a stratified rockshelter deposit in the southern Kalahari Basin, which we date by optically stimulated luminescence to around 105 ka. Uranium-thorium dating of relict tufa deposits indicates sporadic periods of substantial volumes of fresh, flowing water; the oldest of these episodes is dated to between 110 and 100 ka and is coeval with the archaeological deposit. Our results suggest that behavioural innovations among humans in the interior of southern Africa did not lag behind those of populations near the coast, and that these innovations may have developed within a wet savannah environment. Models that tie the emergence of behavioural innovations to the exploitation of coastal resources by our species may therefore require revision.

The first dinosaur egg was soft.

Calcified eggshells protect developing embryos against environmental stress and contribute to reproductive success1. As modern crocodilians and birds lay hard-shelled eggs, this eggshell type has been inferred for non-avian dinosaurs. Known dinosaur eggshells are characterized by an innermost membrane, an overlying protein matrix containing calcite, and an outermost waxy cuticle2-7. The calcitic eggshell consists of one or more ultrastructural layers that differ markedly among the three major dinosaur clades, as do the configurations of respiratory pores. So far, only hadrosaurid, a few sauropodomorph and tetanuran eggshells have been discovered; the paucity of the fossil record and the lack of intermediate eggshell types challenge efforts to homologize eggshell structures across all dinosaurs8-18. Here we present mineralogical, organochemical and ultrastructural evidence for an originally non-biomineralized, soft-shelled nature of exceptionally preserved ornithischian Protoceratops and basal sauropodomorph Mussaurus eggs. Statistical evaluation of in situ Raman spectra obtained for a representative set of hard- and soft-shelled, fossil and extant diapsid eggshells clusters the originally organic but secondarily phosphatized Protoceratops and the organic Mussaurus eggshells with soft, non-biomineralized eggshells. Histology corroborates the organic composition of these soft-shelled dinosaur eggs, revealing a stratified arrangement resembling turtle soft eggshell. Through an ancestral-state reconstruction of composition and ultrastructure, we compare eggshells from Protoceratops and Mussaurus with those from other diapsids, revealing that the first dinosaur egg was soft-shelled. The calcified, hard-shelled dinosaur egg evolved independently at least three times throughout the Mesozoic era, explaining the bias towards eggshells of derived dinosaurs in the fossil record.

Emergent constraint on Arctic Ocean acidification in the twenty-first century.

The ongoing uptake of anthropogenic carbon by the ocean leads to ocean acidification, a process that results in a reduction in pH and in the saturation state of biogenic calcium carbonate minerals aragonite (Ωarag) and calcite (Ωcalc)1,2. Because of its naturally low Ωarag and Ωcalc (refs. 2,3), the Arctic Ocean is considered the region most susceptible to future acidification and associated ecosystem impacts4-7. However, the magnitude of projected twenty-first century acidification differs strongly across Earth system models8. Here we identify an emergent multi-model relationship between the simulated present-day density of Arctic Ocean surface waters, used as a proxy for Arctic deep-water formation, and projections of the anthropogenic carbon inventory and coincident acidification. By applying observations of sea surface density, we constrain the end of twenty-first century Arctic Ocean anthropogenic carbon inventory to 9.0 ± 1.6 petagrams of carbon and the basin-averaged Ωarag and Ωcalc to 0.76 ± 0.06 and 1.19 ± 0.09, respectively, under the high-emissions Representative Concentration Pathway 8.5 climate scenario. Our results indicate greater regional anthropogenic carbon storage and ocean acidification than previously projected3,8 and increase the probability that large parts of the mesopelagic Arctic Ocean will be undersaturated with respect to calcite by the end of the century. This increased rate of Arctic Ocean acidification, combined with rapidly changing physical and biogeochemical Arctic conditions9-11, is likely to exacerbate the impact of climate change on vulnerable Arctic marine ecosystems.

The impact of aragonite saturation variability on shelled pteropods: An attribution study in the California Current System.

Observations from the California Current System (CalCS) indicate that the long-term trend in ocean acidification (OA) and the naturally occurring corrosive conditions for the CaCO3 mineral aragonite (saturation state Ω < 1) have a damaging effect on shelled pteropods, a keystone group of calcifying organisms in the CalCS. Concern is heightened by recent findings suggesting that shell formation and developmental progress are already impacted when Ω falls below 1.5. Here, we quantify the impact of low Ω conditions on pteropods using an individual-based model (IBM) with life-stage-specific mortality, growth, and behavior in a high-resolution regional hindcast simulation of the CalCS between 1984 and 2019. Special attention is paid to attributing this impact to different processes that lead to such low Ω conditions, namely natural variability, long-term trend, and extreme events. We find that much of the observed damage in the CalCS, and specifically >70% of the shell CaCO3 loss, is due to the pteropods' exposure to naturally occurring low Ω conditions as a result of their diel vertical migration (DVM). Over the hindcast period, their exposure to damaging waters (Ω < 1.5) increases from 9% to 49%, doubling their shell CaCO3 loss, and increasing their mortality by ~40%. Most of this increased exposure is due to the shoaling of low Ω waters driven by the long-term trend in OA. Extreme OA events amplify this increase by ~40%. Our approach can quantify the health of pteropod populations under shifting environmental conditions, and attribute changes in fitness or population structure to changes in the stressor landscape across hierarchical time scales.

Meridional overturning circulation conveys fast acidification to the deep Atlantic Ocean.

Since the Industrial Revolution, the North Atlantic Ocean has been accumulating anthropogenic carbon dioxide (CO2) and experiencing ocean acidification, that is, an increase in the concentration of hydrogen ions (a reduction in pH) and a reduction in the concentration of carbonate ions. The latter causes the 'aragonite saturation horizon'-below which waters are undersaturated with respect to a particular calcium carbonate, aragonite-to move to shallower depths (to shoal), exposing corals to corrosive waters. Here we use a database analysis to show that the present rate of supply of acidified waters to the deep Atlantic could cause the aragonite saturation horizon to shoal by 1,000-1,700 metres in the subpolar North Atlantic within the next three decades. We find that, during 1991-2016, a decrease in the concentration of carbonate ions in the Irminger Sea caused the aragonite saturation horizon to shoal by about 10-15 metres per year, and the volume of aragonite-saturated waters to reduce concomitantly. Our determination of the transport of the excess of carbonate over aragonite saturation (xc[CO32-])-an indicator of the availability of aragonite to organisms-by the Atlantic meridional overturning circulation shows that the present-day transport of carbonate ions towards the deep ocean is about 44 per cent lower than it was in preindustrial times. We infer that a doubling of atmospheric anthropogenic CO2 levels-which could occur within three decades according to a 'business-as-usual scenario' for climate change-could reduce the transport of xc[CO32-] by 64-79 per cent of that in preindustrial times, which could severely endanger cold-water coral habitats. The Atlantic meridional overturning circulation would also export this acidified deep water southwards, spreading corrosive waters to the world ocean.

Azoic sediments and benthic foraminifera: Environmental quality in a subtropical coastal lagoon in the gulf of California.

Marine transitional environments play an important role in human sustainability. Around these ecosystems, coastal lagoons are subject to high anthropogenic pressure from population growth. The increased demand for goods and services is associated with the elevated discharge of untreated and treated wastewater into lagoon systems. The absence of benthic organisms in lagoon environments has been linked to extreme natural conditions and severe anthropogenic impact at both spatial and temporal scales. However, the mechanisms that lead to the presence of azoic sediments in lagoon environments have yet to be studied. This study aimed to determine the vertical variability of textural groups, geochemistry, and benthic foraminiferal fauna to understand how natural and anthropogenic components generate a vertical sediment sequence with low or absent benthic foraminifera in a subtropical coastal lagoon in the southwestern end of the Gulf of California. A 41 cm-long sediment core was collected from La Paz Lagoon at a 1-m depth. The core was sectioned every centimeter, and sediment subsamples were dried and homogenized for grain size, calcium carbonate, elemental and isotopic carbon and nitrogen analyses, and benthic foraminifera quantification. Muds with fine sands towards the core's base characterized the sedimentary sequence. Organic carbon and total nitrogen increased from the base (1.4% and 0.06%, respectively) to the core-top (CT, 3.0% and 0.14%, respectively), significant from the 27 cm interval. Calcium carbonate content was very low (<0.8%). The relationship of δ13C vs. C:N ratio indicated that sedimentary organic carbon was derived from the marine and sewage source mixture. The δ15N of organic matter increased by 3.7‰, starting from the 27 cm interval towards the CT. The nitrogen sewage input source was relatively more significant than nitrogen fixation. The few individuals (<18 ind. in 10 g) and genera (Ammonia and Elphidium), as well as the absence of foraminifera in 19 of 41 intervals in the core, indicated that environmental conditions were unfavorable, even for colonization of environmentally stress-tolerant genera. The frequency of azoic sediments was higher from the 25 cm interval to the CT vs. from the base to the 25 cm interval. Moreover, the AEI revealed severe to moderate hypoxia in the study area. The limited presence of benthic foraminifera and calcium carbonate preservation corroborated that the quality of the lagoon's environment has deteriorated along with population growth, which requires strategic programs to sustain this transitional ecosystem.

Limestone water mixing process and hydrogen and oxygen stable isotope fractionation response under mining action.

North China type coalfield are gradually mining deep, and the mixing of groundwater is intensified. Hydrogen and oxygen isotopes are important elements for tracing groundwater movement. The fractionation response mechanism under mining conditions is not clear. In this paper, combined with numerical simulation, MixSIAR isotope mixing model and other methods, according to the δD, δ18O and hydrochemical information of various water bodies, the impact of coal mining on hydrogen and oxygen isotope fractionation is analyzed from multiple perspectives. The results show that summer soil water is the main source of recharge for limestone water, accounting for 30.7%-41.5%, and the Zhan River is the main source of recharge for limestone water. Before groundwater recharge, evaporation leads to the increase of δ18O in surface water by 0.31‰-5.58‰, water loss by 1.81%-28.00%, the increase of δ18O in soil water by 0.47‰-6.33‰, and water loss by 2.74%-35.80%. Compared with the coal mining layer, the degree of hydrogen and oxygen isotope drift and water-rock interaction in the coal mine stopping layer are significantly improved. The results of numerical simulation show that the pumping activity reduces the 18O concentration in the mining layer. The ion ratio is used as a new variable to eliminate the influence of water-rock interaction when calculating the mixing ratio. The results show that the limestone water is in a state of receiving external recharge, and mixing effect increases the δ18O in limestone water by 0.86‰ on average, and the δD increases by 0.72‰ on average. The research results explain the controlled process of hydrogen and oxygen isotope fractionation under mining conditions, which is of great significance to coal mine safety production.

Release and health outcomes of exposure to chalk particles in classrooms: a systematic literature review.

This systematic review explores the release and health outcomes of exposure to chalk particles in classrooms. A literature search was conducted on Scopus, Google Scholar, and the Web of Science. Chalk particles contribute significantly to poor indoor air quality in classrooms. Higher concentrations of PM2.5 chalk particles were found in the front row (14.25 µg/m3) and near the chalkboard (19.07 µg/m3). Inhalation and dermal are significant exposure routes; hence, teachers and learners are at risk of developing respiratory and skin disorders. Inhalation of chalk particles correlates with reduced lung function in teachers and learners. The release and size of chalk particles depend on the activities, type of chalk sticks, and texture of the chalkboards. Wiping the chalkboard releases more chalk particles of smaller size (3.85-9.3 µm) than writing (10.57-92.91 µm). A shift from chalk sticks and chalkboards in classrooms is necessary to mitigate the associated health risks.

Identifying sources of acid mine drainage and major hydrogeochemical processes in abandoned mine adits (Southeast Shaanxi, China).

Acid mine drainage (AMD) has resulted in significant risks to both human health and the environment of the Han River watershed. In this study, water and sediment samples from typical mine adits were selected to investigate the hydrogeochemical characteristics and assess the environmental impacts of AMD. The interactions between coexisting chemical factors, geochemical processes in the mine adit, and the causes of AMD formation are discussed based on statistical analysis, mineralogical analysis, and geochemical modeling. The results showed that the hydrochemical types of AMD consisted of SO4-Ca-Mg, SO4-Ca, and SO4-Mg, with low pH and extremely high concentrations of Fe and SO42-. The release behaviors of most heavy metals are controlled by the oxidation of sulfide minerals (mainly pyrite) and the dissolution/precipitation of secondary minerals. Along the AMD pathway in the adit, the species of Fe-hydroxy secondary minerals tend to initially increase and later decrease. The inverse model results indicated that (1) oxidative dissolution of sulfide minerals, (2) interconversion of Fe-hydroxy secondary minerals, (3) precipitation of gypsum, and (4) neutralization by calcite are the main geochemical reactions in the adit, and chlorite might be the major neutralizing mineral of AMD with calcite. Furthermore, there were two sources of AMD in abandoned mine adits: oxidation of pyrite within the adits and infiltration of AMD from the overlying waste rock dumps. The findings can provide deeper insight into hydrogeochemical processes and the formation of AMD contamination produced in abandoned mine adits under similar mining and hydrogeological conditions.

Geochemical, mineralogical records, and statistical approaches in establishing sedimentary in the environment of a Mediterranean coastal system: case of Sebkha El-Guettiate (southeastern Tunisia).

The current study was conducted within the context of the Holocene era in Sebkha El-Guettiate, located in southeastern Tunisia. The aim was to determine the factors influencing the geochemical and mineralogical composition of sediments and to elucidate the sedimentary characteristics of the Holocene within the Sebkha core. We examined a sediment core extending 100 cm from this Sebkha, subjecting it to comprehensive analysis to uncover its sedimentological, mineralogical, and geochemical properties. Several techniques were employed to strengthen and validate the connections between geochemical and mineralogical analyses, including X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), and infrared (IR) spectroscopy, among others. Furthermore, statistical analyses utilizing principal component analysis (PCA) were applied to the results of the geochemical and mineralogical studies, aiding in the identification of patterns and relationships. A comprehensive mineralogical assessment of the core's sediments revealed the presence and interpretation of carbonate minerals, evaporite minerals, and detrital minerals. Through the application of infrared (IR) spectrometer techniques to all sediment samples, we gained insight into the mineralogical components and the distribution of key elements such as quartz, kaolinite, calcite, feldspar, and organic carbon. The geochemical composition demonstrated a clear dominance of silica (SiO2), accompanied by fluctuations in carbonate percentages (CaCO3). The prominent major elements, primarily magnesium (Mg) and calcium (Ca) originating from dolomitization, sodium (Na) and chlorine (Cl) from halite, and calcium (Ca) from gypsum, exhibited varying levels. Results from Rock-Eval 6 pyrolysis indicated that the organic matter within the sediments is generally a mixture of terrestrial and aquatic origins. This study provides practical information that underscores the diverse origins contributing to Sebkha sediment formation, often influenced by saline systems.

Directional fabrication and dissolution of larval and juvenile oyster shells under ocean acidification.

Biomineralization is one of the key biochemical processes in calcifying bivalve species such as oysters that is affected by ocean acidification (OA). Larval life stages of oysters are made of aragonite crystals whereas the adults are made of calcite and/or aragonite. Though both calcite and aragonite are crystal polymorphs of calcium carbonate, they have different mechanical properties and hence it is important to study the micro and nano structure of different life stages of oyster shells under OA to understand the mechanisms by which OA affects biomineralization ontogeny. Here, we have studied the larval and juvenile life stages of an economically and ecologically important estuarine oyster species, Crassostrea hongkongensis, under OA with focus over shell fabrication under OA (pHNBS 7.4). We also look at the effect of parental exposure to OA on larvae and juvenile microstructure. The micro and nanostructure characterization reveals directional fabrication of oyster shells, with more organized structure as biomineralization progresses. Under OA, both the larval and juvenile stages show directional dissolution, i.e. the earlier formed shell layers undergo dissolution at first, owing to longer exposure time. Despite dissolution, the micro and nanostructure of the shell remains unaffected under OA, irrespective of parental exposure history.

The structure of the eggshell and eggshell membranes of Crocodylus niloticus.

The macro- and microstructure, elemental composition, and crystallographic characteristics of the eggshell and eggshell membranes of the Crocodylus niloticus egg was investigated using optical and electron microscopy, energy-dispersive X-ray spectroscopy (EDS), electron backscatter diffraction (EBSD) and computerised tomography. The translucent ellipsoid egg is composed of two basic layers, the outer calcified layer referred to as the shell and an inner organic fibre layer, referred to as the shell membrane. The outer inorganic calcite shell is further divided into an external, palisade and mammillary layers with pore channels traversing the shell. The external layer is a thin layer of amorphous calcium and phosphorus, the underlying palisade layer consist of irregular wedge-shaped crystals composed calcite with traces of magnesium, sodium, sulphur and phosphorus. The crystals are mostly elongated, orientated perpendicular to the shell surface ending in cone-shaped knobs, which forms the inner mammillary layer. The elemental composition of the mammillae is like that of the palisade layer, but the crystal structure is much smaller and orientated randomly. The highest number of mammillae and shell pores are found at the equator of the egg, becoming fewer towards the egg poles. The shell thickness follows the same pattern, with the thickest area located at the equator. The eggshell membrane located right beneath and embedded in the mammillary layer of the shell; it is made up of unorganised fibre sheets roughly orientated at right angles to one another. Individual fibres consist of numerous smaller fibrils forming open channels that run longitudinally through the fibre.

Integration of hydrogeological data, GIS and AHP techniques applied to delineate groundwater potential zones in sandstone, limestone and shales rocks of the Damoh district, (MP) central India.

The Damoh district, which is located in the central India and characterized by limestone, shales, and sandstone compact rock. The district has been facing groundwater development challenges and problems for several decades. To facilitate groundwater management, it is crucial to monitoring and planning based on geology, slope, relief, land use, geomorphology, and the types of the basaltic aquifer in the drought-groundwater deficit area. Moreover, the majority of farmers in the area are heavily dependent on groundwater for their crops. Therefore, delineation of groundwater potential zones (GPZ) is essential, which is defined based on various thematic layers, including geology, geomorphology, slope, aspect, drainage density, lineament density, topographic wetness index (TWI), topographic ruggedness index (TRI), and land use/land cover (LULC). The processing and analysis of this information were carried out using Geographic Information System (GIS) and Analytic Hierarchy Process (AHP) methods. The validity of the results was trained and tested using Receiver Operating Characteristic (ROC) curves, which showed training and testing accuracies of 0.713 and 0.701, respectively. The GPZ map was classified into five classes such as very high, high, moderate, low, and very low. The study revealed that approximately 45% of the area falls under the moderate GPZ, while only 30% of the region is classified as having a high GPZ. The area receives high rainfall but has very high surface runoff due to no proper developed soil and lack of water conservation structures. Every summer season show a declined groundwater level. In this context, results of study area are useful to maintain the groundwater under climate change and summer season. The GPZ map plays an important role in implementing artificial recharge structures (ARS), such as percolation ponds, tube wells, bore wells, cement nala bunds (CNBs), continuous contour trenching (CCTs), and others for development of ground level. This study is significant for developing sustainable groundwater management policies in semi-arid regions, that are experiencing climate change. Proper groundwater potential mapping and watershed development policies can help mitigate the effects of drought, climate change, and water scarcity, while preserving the ecosystem in the Limestone, Shales, and Sandstone compact rock region. The results of this study are essential for farmers, regional planners, policy-makers, climate change experts, and local governments, enabling them to understand the groundwater development possibilities in the study area.

Groundwater pollutants characterization by geochemometric technique and geochemical modeling in tropical savanna watershed.

Multiple interactions of geogenic and anthropogenic activities can trigger groundwater pollution in the tropical savanna watershed. These interactions and resultant contamination have been studied using applied geochemical modeling, conventional hydrochemical plots, and multivariate geochemometric methods, and the results are presented in this paper. The high alkalinity values recorded for the studied groundwater samples might emanate from the leaching of carbonate soil derived from limestone coupled with low rainfall and high temperature in the area. The principal component analysis (PCA) unveils three components with an eigenvalue > 1 and a total dataset variance of 67.37%; this implies that the temporary hardness of the groundwater and water-rock interaction with evaporite minerals (gypsum, halite, calcite, and trona) is the dominant factor affecting groundwater geochemistry. Likewise, the PCA revealed anthropogenic contamination by discharging [Formula: see text] [Formula: see text][Formula: see text] and [Formula: see text] from agricultural activities and probable sewage leakages. Hierarchical cluster analysis (HCA) also revealed three clusters; cluster I reflects the dissolution of gypsum and halite with a high elevated load of [Formula: see text] released by anthropogenic activities. However, cluster II exhibited high [Formula: see text] and [Formula: see text] loading in the groundwater from weathering of bicarbonate and sylvite minerals. Sulfate ([Formula: see text]) dominated cluster III mineralogy resulting from weathering of anhydrite. The three clusters in the Maiganga watershed indicated anhydrite, gypsum, and halite undersaturation. These results suggest that combined anthropogenic and natural processes in the study area are linked with saturation indexes that regulate the modification of groundwater quality.

Comparative assessment of soil fertility across varying elevations.

Land elevation exerts a significant influence on soil fertility through affecting macro and micro climatic conditions and geomorphological processes. To evaluate the soil fertility at different elevation classes, namely 1600-2000, 2000-2400, 2400-2800, and > 2800 m, 350 surface soil samples (0-30 cm) were collected from the agricultural lands of northwestern Iran. Soil properties, including soil texture, calcium carbonate (CaCO3), pH, electrical conductivity (EC), organic matter (OM), and soil macronutrients (TN, P, and K) and micronutrients (Fe, Mn, Zn, and Cu), were measured. Finally, the interpretation and classification of the soil samples were made using the nutritional value index (NIV). The comparison of the NIV index based on elevation changes showed that the Gomez method classifies the soil properties in an optimal order as evidenced by its tendency towards the center of the data. However, the Common method is more consistent with the observed trend. After classifying the NIV index using the Common method, it was determined that CaCO3 and soil salinity are not the limiting factor for soil fertility in different elevation classes. However, in all elevations, high pH, low OM at elevations > 2800 m, total nitrogen (TN), available phosphorous (AP), and micronutrients deficiencies, except Zn at the elevation of 1600-2000 m, are the main limiting factors for soil fertility of agricultural lands. The results provide further insight into the elevation-based land evaluation and may supports grower's decision on nutrient management and crop selection strategies.

Assessment of 222Rn, 226Ra, 238U, 218Po, and 214Po activity concentrations in the blood samples of workers at selected building material factories in Erbil City.

The objective of this research is to assess the impact of radon concentration on workers at certain construction material industries in Erbil, Kurdistan Region of Iraq. The CR-39 solid-state track detector was used in this experiment to monitor radon levels and their daughters. For this purpose, as a case study group, 70 workers were divided into seven subgroups (gypsum, cement plant, lightweight block, marble, red brick 1, crusher stone, and concrete block 2), and 20 healthy volunteers were selected as a control group. The findings demonstrate that the mean concentrations of radon, radium, uranium, and radon daughters deposited on the detector face (POS) and chamber walls (POW) for the case study group were 9.61 ± 1.52 Bq/m3, 0.33 ± 0.05 Bq/Kg, 5.39 ± 0.86 mBq/Kg, 4 ± 0.63, and 16.62 ± 2.64 mBq/m3, whereas for the control group, they were 3.39 ± 0.58 Bq/m3, 0.117 ± 0.03 Bq/Kg, 1.91 ± 0.32 mBq/Kg, 1.41 ± 0.24, and 5.88 ± 1 mBq/m3, respectively. The statistical analysis revealed that radon, radium, uranium, and POW and POS concentrations were statistically significant (p ≤ 0.001) in the samples for the case study groups of cement, lightweight block, red brick 1, marble, and crusher stone factories in comparison to the control group; however, the results for gypsum and concrete block 2 factories were not statistically significant in comparison to the control group. Intriguingly, the radon levels in every blood sample examined were far lower than the 200 Bq/m3 limit established by the International Atomic Energy Agency. Hence, it may be argued that the blood is devoid of contaminants. These results are crucial for determining whether or not an individual is exposed to substantial quantities of radiation and for demonstrating a link between radon, its daughter, uranium, and the prevalence of cancer among workers in the Kurdish region of Iraq.

Pedological data for the study of soils developed over a limestone bed in a humid tropical environment.

Lithological characteristics interact with other factors of soil formation to define soil genesis. This becomes more interesting as data on the mineral and elemental oxide components of soils developed from limestone are rarely available in the humid tropical environment. The present study investigated the elemental oxide content, forms of sesquioxides, and clay mineral species in some limestone soils. Soil samples were obtained from three (3) crestal soil profile pits and analyzed for elemental content by the use of an X-ray fluorescence spectrometer, and sesquioxide forms by inductively coupled plasma-mass spectrometer. Analyses were done in triplicates. The mineralogy of the clay fraction was determined on the A, B, and C horizon samples using an X-ray diffraction technique. The occurrence of SiO2 (203-277 g/kg), Al2O3 (65-105 g/kg), and Fe2O3 (14-95 g/kg) in substantial amounts over MnO2, ZrO2, and TiO2 with negligible quantities of CaO suggested comparatively more developed soils in the Agoi Ibami and Mfamosing tropical rainforests. Crystalline form of Fe was dominant over amorphous form, with indications of the co-migration of dithionite Fe with clay to the B horizons of the soils. Quartz, kaolinite, montmorillonite, and chlorite-vermiculite-montmorillonite interlayered minerals dominated the clay mineralogy of the studied soils. Mineral transformation places the soils at the transitory stage from the intermediate to the complete stage of soil development. The expanding clay minerals are most likely to increase plant nutrient adsorption and soil fertility status to accommodate the cultivation of a wider range of crops.

Variation and multi-time series prediction of total hardness in groundwater of the Guanzhong Plain (China) using grey Markov model.

Total hardness (TH) is an important index representing the water suitability for domestic purpose. TH is represented mainly by Ca2+ and Mg2+ which are essential elements for human bone development. Between 2000 and 2015, the TH values of groundwater in major cities of the Guanzhong Plain varied significantly. The study was carried out to investigate TH variation over 16 years and to examine how effective the grey Markov model was in predicting TH concentrations in time series datasets. The hydrochemical parameters determining TH concentration and their origins were investigated using statistical analysis and geochemical models. The grey Markov model, which is effective in short time series prediction, was used to forecast the multi-time series of TH. The findings demonstrated a prevalence of HCO3- and SO42- in the groundwater types combined with calcite precipitation, gypsum, and dolomite dissolution that increased the concentration of Ca2+, Mg2+, and HCO3-, influencing TH variation. The predicted TH values of the eight monitoring wells for the year 2016 were 1213.66, 124.30, 203.66, 103.01, 349.56, 251.23, 453.31, and 471.81 mg/L, respectively. Datasets with low TH variation were more accurately predicted than datasets with high TH variation. This was especially observed on sample B557 where TH concentration in 2010 was 400.33 mg/L and suddenly dropped to 90.1, 82.6, 85.1, 87.6, and 75.1 mg/L in 2011, 2012, 2013, 2014, and 2015, respectively. The study also shows that the Markov chain model can optimize the GM(1,1) model and improve the prediction accuracy significantly. All samples in Weinan City and one sample in Xi'an City showed a significant decrease in TH concentration. Except one sample in Xi'an City, TH concentrations tended to rise in the other cities (Baoji, Xianyang) of the Guanzhong Plain. This study verified the reliability of the grey Markov model in terms of forecasting time series datasets with high variability, and the results can be referential to similar studies in the world.

Nitrate Removal by a Novel Lithoautotrophic Nitrate-Reducing, Iron(II)-Oxidizing Culture Enriched from a Pyrite-Rich Limestone Aquifer.

Nitrate removal in oligotrophic environments is often limited by the availability of suitable organic electron donors. Chemolithoautotrophic bacteria may play a key role in denitrification in aquifers depleted in organic carbon. Under anoxic and circumneutral pH conditions, iron(II) was hypothesized to serve as an electron donor for microbially mediated nitrate reduction by Fe(II)-oxidizing (NRFeOx) microorganisms. However, lithoautotrophic NRFeOx cultures have never been enriched from any aquifer, and as such, there are no model cultures available to study the physiology and geochemistry of this potentially environmentally relevant process. Using iron(II) as an electron donor, we enriched a lithoautotrophic NRFeOx culture from nitrate-containing groundwater of a pyrite-rich limestone aquifer. In the enriched NRFeOx culture that does not require additional organic cosubstrates for growth, within 7 to 11 days, 0.3 to 0.5 mM nitrate was reduced and 1.3 to 2 mM iron(II) was oxidized, leading to a stoichiometric NO3-/Fe(II) ratio of 0.2, with N2 and N2O identified as the main nitrate reduction products. Short-range ordered Fe(III) (oxyhydr)oxides were the product of iron(II) oxidation. Microorganisms were observed to be closely associated with formed minerals, but only few cells were encrusted, suggesting that most of the bacteria were able to avoid mineral precipitation at their surface. Analysis of the microbial community by long-read 16S rRNA gene sequencing revealed that the culture is dominated by members of the Gallionellaceae family that are known as autotrophic, neutrophilic, and microaerophilic iron(II) oxidizers. In summary, our study suggests that NRFeOx mediated by lithoautotrophic bacteria can lead to nitrate removal in anthropogenically affected aquifers. IMPORTANCE Removal of nitrate by microbial denitrification in groundwater is often limited by low concentrations of organic carbon. In these carbon-poor ecosystems, nitrate-reducing bacteria that can use inorganic compounds such as Fe(II) (NRFeOx) as electron donors could play a major role in nitrate removal. However, no lithoautotrophic NRFeOx culture has been successfully isolated or enriched from this type of environment, and as such, there are no model cultures available to study the rate-limiting factors of this potentially important process. Here, we present the physiology and microbial community composition of a novel lithoautotrophic NRFeOx culture enriched from a fractured aquifer in southern Germany. The culture is dominated by a putative Fe(II) oxidizer affiliated with the Gallionellaceae family and performs nitrate reduction coupled to Fe(II) oxidation leading to N2O and N2 formation without the addition of organic substrates. Our analyses demonstrate that lithoautotrophic NRFeOx can potentially lead to nitrate removal in nitrate-contaminated aquifers.