Controls on Cyclic Formation of Quaternary Early Diagenetic Dolomite

The origin of sedimentary dolomite and the factors that control its formation within the geological record remain speculative. In most models, dolomite formation is linked to evaporative conditions, high water temperature, increasing Mg/Ca ratio, increasing alkalinity, and high amounts of biomass. Here we challenge these archetypal views, by documenting a case example of Quaternary dolomite which formed in Lake Van at constantly low temperature (<4°C) and without direct control of the latter conditions. Dolomite occurs within highstand sediments related to suborbital climate variability (Dansgaard‐Oeschger cycles). We propose that dolomite precipitation is a product of a microbially influenced process, triggered by ecological stress, resulting from reventilation of the water‐sediment interface. Independently from the validity of this hypothesis, our results call for a reevaluation of the paleoenvironmental conditions often invoked for early diagenetic dolomite‐rich intervals within sedimentary sequences and for caution when interpreting time series of subrecent lacustrine carbonates

Ca-looping for postcombustion CO2 capture: A comparative analysis on the performances of dolomite and limestone

The low cost and wide availability of natural limestone (CaCO3) is at the basis of the industrial competitiveness of the Ca-looping (CaL) technology for postcombustion CO2 capture as already demonstrated by ~1Mwt scale pilot projects. A major focus of studies oriented towards further improving the efficiency of the CaL technology is how to prevent the gradual loss of capture capacity of limestone derived CaO as the number of carbonation/calcination cycles is increased. Natural dolomite (MgCa(CO3)2) has been proposed as an alternative sorbent precursor to limestone. Yet, carbonation of MgO is not thermodynamically favorable at CaL conditions, which may hinder the capture performance of dolomite. In the work described in this paper we carried out a thermogravimetric analysis on the multicyclic capture performance of natural dolomite under realistic regeneration conditions necessarily implying high calcination temperature, high CO2 concentration and fast transitions between the carbonation and calcination stages. Our study demonstrates that the sorbent derived from dolomite has a greater capture capacity as compared to limestone. SEM analysis shows that MgO grains in the decomposed dolomite are resistant to sintering under severe calcination conditions and segregate from CaO acting as a thermally stable support which mitigates the multicyclic loss of CaO conversion. Moreover, full decomposition of dolomite is achieved at significantly lower calcination temperatures as compared to limestone, which would help improving further the industrial competitiveness of the technology.Junta de Andalucía FQM-5735, TEP-7858, TEP-1900Ministerio de Economía y Competitividad FIS2011-25161, CTQ2011- 2762

Discriminating cool-water from warm-water carbonates and their diagenetic environments using element geochemistry: the Oligocene Tikorangi Formation (Taranaki Basin) and the dolomite effect

Fields portrayed within bivariate element plots have been used to distinguish between carbonates formed in warm- (tropical) water and cool- (temperate) water depositional settings. Here, element concentrations (Ca, Mg, Sr, Na, Fe, and Mn) have been determined for the carbonate fraction of bulk samples from the late Oligocene Tikorangi Formation, a subsurface, mixed dolomite-calcite, cool-water limestone sequence in Taranaki Basin, New Zealand. While the occurrence of dolomite is rare in New Zealand Cenozoic carbonates, and in cool-water carbonates more generally, the dolomite in the Tikorangi carbonates is shown to have a dramatic effect on the "traditional" positioning of cool-water limestone fields within bivariate element plots. Rare undolomitised, wholly calcitic carbonate samples in the Tikorangi Formation have the following average composition: Mg 2800 ppm; Ca 319 100 ppm; Na 800 ppm; Fe 6300 ppm; Sr 2400 ppm; and Mn 300 ppm. Tikorangi Formation dolomite-rich samples (>15% dolomite) have average values of: Mg 53 400 ppm; Ca 290 400 ppm; Na 4700 ppm; Fe 28 100 ppm; Sr 5400 ppm; and Mn 500 ppm. Element-element plots for dolomite-bearing samples show elevated Mg, Na, and Sr values compared with most other low-Mg calcite New Zealand Cenozoic limestones. The increased trace element contents are directly attributable to the trace element-enriched nature of the burial-derived dolomites, termed here the "dolomite effect". Fe levels in the Tikorangi Formation carbonates far exceed both modern and ancient cool-water and warm-water analogues, while Sr values are also higher than those in modern Tasmanian cool-water carbonates, and approach modern Bahaman warm-water carbonate values. Trace element data used in conjunction with more traditional petrographic data have aided in the diagenetic interpretation of the carbonate-dominated Tikorangi sequence. The geochemical results have been particularly useful for providing more definitive evidence for deep burial dolomitisation of the deposits under the influence of marine-modified pore fluids

Evidence of microbial activity from a shallow water whale fall (Voghera, northern Italy)

The fossil bones, associated carbonate cements and enclosing concretion of a Miocene mysticete from inner shelf deposits (Monte Vallassa Formation, northern Italy) were analyzed for evidence of microbial activity. Optical and scanning electron microscopy, Raman spectroscopy, and stable C and O isotope geochemistry were used for high spatial resolution microfacies and biosedimentological analyses. Whale cancellous bones were filled by different carbonate cements including microcrystalline dolomite, rhombohedral dolomite and sparry calcite. Biofabric and biominerals such as microbial peloids, clotted textures and pyrite framboids were associated with the dolomite cements. Dolomite inside cancellous bones and in the enclosing concretion showed similar isotopic values (avg δ 13C: -7.12‰; avg δ 18O: +3.81‰), depleted with respect to the (late) sparry calcite cement (avg δ 13C: -0.55‰; avg δ 18O: -0.98‰). Microcrystalline barite (BaSO 4) was observed on the external surface of the bones. In addition, two different types of microborings were recognized, distinguished by their size and morphology and were ascribed respectively to prokaryote and fungal trace makers. Our results testify for the development of a diverse microbial ecosystem during the decay of a shallow water whale carcass, which could be detected in the fossil record. However, none of the observed biosignatures (e.g., microbial peloids, clotted textures) can be used alone as a positive fossil evidence of the general development of a sulfophilic stage of whale fall ecological succession. The occurrence of the hard parts of chemosynthetic invertebrates associated with fossil whale bones is still the more convincing proof of the development of a sulfide-base chemoautotrophic ecosystem. © 2011 Elsevier B.V

The role of limestone and dolomite tailings’ particle size in retention of heavy metals from liquid waste

Purpose. The study aims at investigating the role of particle size of mineral tailings derived from limestone, limestone marble, dolomite and dolomitic marble in heavy metal adsorption, in both batch and fixed bed conditions, so as to estimate whether grinding and/or sieving is necessary for their utilization. Methods. Fractions of different particle size have been studied. Adsorption has been examined in batch conditions from solutions of 5 mg/l Cd, 5 mg/l Pb, 100 mg/l Cu, 100 mg/l Zn, and their mixed solution simulating electroplating wastewater, and also in fixed bed conditions. Findings. Total Cd and Cu adsorption is achieved on all the mineral fractions, whereas Pb and Zn show a difference up to 20% depending on particle size. Referring to the mixed solution, Cd and Zn adsorption is lower, whereas no significant differences in Cu and Pb adsorption are observed. Adsorption capacity rises up to 0.03 mg/g Cd, 0.60 mg/g Cu, 0.03 mg/g Pb, 0.60 mg/g Zn. In fixed bed conditions, metal adsorption greater than 93% is achieved. Furthermore, leaching not exceeding 4% indicates a good metal retention. Finally, Taguchi method has proven that the particle size effect is not so strong compared to other parameters, including solution concentration and time. Originality. The particle size of mineral tailings has not yet been investigated as a parameter affecting heavy metal adsorption. Furthermore, heavy metal adsorption has been examined from separate metal solutions and not from a mixed one. The present study aims at contributing to these two research fields. Practical implications. Τhe differences in adsorption between mineral tailings’ fractions with different particle size are not as high as to make grinding of minerals necessary.Мета. Дослідження впливу розмірів частинок у хвостах збагачення вапняку, вапняного мармуру, доломіту та доломітового мармуру на процес адсорбції важких металів у нерухомому шарі для оцінки доцільності технології подрібнення й/або просіювання в подальшому використанні металів. Методика. Для виконання досліджень зразки вапняку та доломіту доставлені компанією, що займається виробництвом і продажем готових бетонів, а також кар’єрами у Греції. Хімічний і мінералогічний склад зразків був визначений рентгенівської флуоресценцією (XRF, ARL ADVANT XP), рентгенівської дифракцією (XRD, Siemens D-500) та атомно-абсорбційною спектрометрією (AAS, VARIAN AA240FS). Для дослідження механізму адсорбції були виміряні наступні параметри: рН відповідно до ISO 6588, пористість і питома площа поверхні за допомогою N2-адсорбції (NOVA-2200, версія 6.11) та катіонообмінна ємність (CEC) відповідно до EPA 9081 на основі змішування зразка з надлишком розчину ацетату натрію, в результаті якого потім визначались додані катіони натрію для матричних катіонів. Для сорбційних експериментів були використані окремі розчини, які містять 5 мг/л Cd, 5 мг/л Pb, 100 мг/л Cu, 100 мг/л Zn, отримані з аналітичних стандартних розчинів Fluka. Після сорбційних досліджень зібрані сорбенти були піддані дослідженням вилуговування. Результати. У процесі досліджень була досягнута повна адсорбція Cd і Cu з усіх мінеральних фракцій, проте до 20% адсорбції Pb і Zn визначалася розмірами частинок. Встановлено, що величина адсорбції Cd і Zn нижче у змішаному розчині, але при цьому даний показник для Cu і Pb залишається без змін. Поглинаюча здатність зростає до 0.03 мг/г Cd, 0.60 мг/г Cu, 0.03 мг/г Pb, 0.60 мг/г Zn. В умовах нерухомого шару досягається до 93% адсорбції металів. Більше того, витік, що не перевищує 4%, свідчить про ефективність вилучення металів. Доведено за методом Тагучі, що вплив розмірів частинок не є настільки значним, щоб не враховувати роль інших параметрів, таких як концентрація розчину і час. Вилуговування іонів металів (Cd, Cu, Pb, Zn), що зберігаються на всіх мінералах після адсорбції в періодичних умовах, не перевищує 4% та вказує на те, що вони досить зберігаються на поверхні мінералів. Це є важливим результатом для подальшого використання мінералів у якості субстратів на полігонах. Наукова новизна. Вперше розміри частинок у хвостах збагачення мінералів розглянуті як параметр, який впливає на процес адсорбції важких металів, при цьому даний процес вивчений також щодо окремих розчинів металів, а не тільки їх суміші. Практична значимість. Виявленні відмінності у показниках адсорбції для фракцій частинок різного розміру не такі значущі, щоб обумовлювати необхідність їх подрібнення в технологічному процесі.Цель. Исследование влияния размеров частиц в хвостах обогащения известняка, известкового мрамора, доломита и доломитового мрамора на процесс адсорбции тяжелых металлов в неподвижном слое для оценки целесообразности технологии измельчения и/или просеивания в дальнейшем использования металлов. Методика. Для выполнения исследований образцы известняка и доломита доставлены компанией, занимающейся производством и продажей готовых бетонов, а также карьерами в Греции. Химический и минералогический состав образцов был определен рентгеновской флуоресценцией (XRF, ARL ADVANT XP), рентгеновской дифракцией (XRD, Siemens D-500) и атомно-абсорбционной спектрометрией (AAS, VARIAN AA240FS). Для исследования механизма адсорбции были измерены следующие параметры: рН в соответствии с ISO 6588, пористость и удельная площадь поверхности с помощью N2-адсорбции (NOVA-2200, версия 6.11) и катионообменная емкость (CEC) в соответствии с EPA 9081 на основе смешивания образца с избытком раствора ацетата натрия, в результате которого затем определялись добавленные катионы натрия для матричных катионов. Для сорбционных экспериментов были использованы отдельные растворы, содержащие 5 мг/л Cd, 5 мг/л Pb, 100 мг/л Cu, 100 мг/л Zn, полученные из аналитических стандартных растворов Fluka. После сорбционных исследований собранные сорбенты были подвергнуты исследованиям выщелачивания. Результаты. В процессе исследований была достигнута полная адсорбция Cd и Cu из всех минеральных фракций, однако до 20% адсорбции Pb и Zn определялась размерами частиц. Установлено, что величина адсорбции Cd и Zn ниже в смешанном растворе, но при этом данный показатель для Cu и Pb остается без изменений. Поглощающая способность возрастает до 0.03 мг/г Cd, 0.60 мг/г Cu, 0.03 мг/г Pb, 0.60 мг/г Zn. В усло-виях неподвижного слоя достигается до 93% адсорбции металлов. Более того, утечка, не превышающая 4%, свидетельствует об эффективности извлечения металлов. Доказано по методу Тагучи, что влияние размеров частиц не является настолько значительным, чтобы не учитывать роль других параметров, таких как концентрация раствора и время. Выщелачивание ионов металлов (Cd, Cu, Pb, Zn), сохраняющихся на всех минералах после адсорбции в периодических условиях, не превышает 4% и указывает на то, что они достаточно сохраняются на поверхности минералов. Это является важным результатом для дальнейшего использования минералов в качестве субстратов на полигонах. Научная новизна. Впервые размеры частиц в хвостах обогащения минералов рассмотрены как параметр, оказывающий влияние на процесс адсорбции тяжелых металлов, при этом данный процесс изучен также в отношении отдельных растворов металлов, а не только их смеси. Практическая значимость. Выявленные различия в показателях адсорбции для фракций частиц различного размера не столь значимы, чтобы обусловливать необходимость их измельчения в технологическом процессе.The present study did not originate under any of project and no funding was raised for research. However, we would like to thank especially Professor Angeliki Moutsatsou and the personal of the Laboratory of Inorganic and Analytical Chemistry of the Chemical Engineering School in the National Technical University of Athens for their various support during the experimental work required for the successful realization of the present study

Effect of impurities and sintering temperature on properties of MgO-CaZrO3 ceramic

CaZrO3 -MgO ceramics are useful as refractories in kilns for the cement production. One method of manufacture of such ceramics is by sintering from m-ZrO2 and dolomite MgCa(CO3 )2 mixtures. In this work electrofused m-ZrO2 grains (fraction <M325) and two Argentinean dolomites with different mineralogical compositions were used as raw materials. Ceramics were obtained by the conventional powder method of uniaxial pressing and subsequent sintering at 1400 to 1680 °C. The influence of the different mineralogy of the dolomites and sintering temperature on the properties of the composites was investigated. Ceramics had 20-30% porosity with representative SEM-EDX microstructure constituted by CaZrO3 agglomerates of variable size (~100µm) and MgO grains (size <50µm) containing some unreacted m-ZrO2 grains. The elastic modulus and flexural strength were correlated with the presence of impurities of the dolomite, porosity and microstructure of the ceramic.Fil: Booth, Raul Fernando Nicolas. Provincia de Buenos Aires. Gobernación. Comision de Invest.científicas. Centro de Tecnología de Recursos Minerales y Ceramica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - la Plata. Centro de Tecnología de Recursos Minerales y Ceramica; ArgentinaFil: Garrido, Liliana Beatriz. Provincia de Buenos Aires. Gobernación. Comision de Invest.científicas. Centro de Tecnología de Recursos Minerales y Ceramica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - la Plata. Centro de Tecnología de Recursos Minerales y Ceramica; ArgentinaFil: Aglietti, Esteban Fausto. Provincia de Buenos Aires. Gobernación. Comision de Invest.científicas. Centro de Tecnología de Recursos Minerales y Ceramica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - la Plata. Centro de Tecnología de Recursos Minerales y Ceramica; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas; Argentin

Refining the interpretation of lacustrine carbonate isotope records: Implications of a mineralogy-specific Lake Van case study

Oxygen and carbon isotope (δ18O and δ13C) data from bulk carbonates are widely applied proxies for temperature, the precipitation/evaporation ratio and productivity in lacustrine palaeohydrology and palaeoclimatology. In case of the terminal and alkaline Lake Van, however, previous studies have shown that bulk oxygen isotope compositions are in disagreement with other proxies when interpreted in a conventional manner. Similarly, the reports on the nature and the timing and site of carbonate precipitation in Lake Van are inconsistent. This study provides evidence on the mineralogy (X-ray powder diffraction analysis, scanning electron microscope imaging, confocal Raman microscopy, electron microprobe analysis) and isotope composition (δ18O and δ13C) of non-skeletal carbonate minerals in a Lake Van sedimentary profile spanning the last ca. 150 kyr. Carbonate phases present in the sediment include aragonite, low-Mg calcite, and calcian dolomite. Dolomite forms as an early diagenetic phase and occurs episodically in high concentrations driving the bulk isotope record towards the higher dolomite δ18O and varying δ13C values. Aragonite and low-Mg calcite precipitate in the surface water and are present in the sediments in varying amounts (relative aragonite to calcite content for dolomite-poor samples Ar/(Ar + Cc) of 93 to 41 wt%). In an attempt to explain this variation, we revised a precipitation model based on annually laminated sediments containing both aragonite and calcite spatially separated in light and dark coloured laminae, respectively. According to our model, spring calcite precipitation, under close-to-freshwater conditions, is followed by evapoconcentration-driven aragonite precipitation in late summer. The precipitation of these carbonate polymorphs from chemically differing surface waters (i.e. freshwater-influenced and evapoconcentrated) leads to distinctly different oxygen and carbon isotope signatures between sedimentary penecontemporaneous aragonite and calcite. The δ18O and δ13C values of aragonite relative to calcite are significantly higher by several per mille than inferred from aragonite-calcite fractionation factors alone, suggesting that the generalised assumption of sedimentary coeval calcite and aragonite precipitating from water with the same isotopic composition is flawed. The here proposed revised hydrologically-separated carbonate precipitation model is not only taking (i) differences in the isotopic fractionation between carbonate minerals into account, but also (ii) considering the hydrological conditions and the processes favouring the precipitation of a given mineral and ultimately controlling its isotopic composition. If mixed mineralogies are present, this mineralogy-specific approach has the potential of refining environmental reconstructions and reconciling apparently equivocal interpretations of different proxy records

Mineral reconnaissance at the Highland boundary with special reference to the Loch Lomond and Aberfoyle areas

Serpentinite bodies at the Highland Boundary in the Loch Lomond and Aberfoyle areas are extensively altered to magnesite-quartz and ferroan-dolomite-quartz rocks. Silicification was probably initiated before conversion to carbonate. Relict textures indicate that the serpentinites were derived from peridotitic precursors, but one unaltered ultrabasic sample comprises mainly chromian diopside. Chromite geochemistry and hornblende-schist mineralogy rein force the ophiolitic character of the serpentinite-spilite-blackshale- chcrt assemblage of the Highland Border. Magnetic and VLF traverses across the Highland Boundary fracture-zone near Helensburgh identified several anomalous zones. One may be due to a concealed serpentinitic sheet. The most mineralised serpentinite body showed chromium values in the range 1000 to 3035 ppm. Such concentrations arc not encouraging for the small serpentinites at Loch Lomond and Aberfoyle, but may be significant regarding larger serpentinites elsewhere at the Highland Border

Stratabound arsenic and vein antimony mineralisation in Silurian greywackes at Glendinning, south Scotland

Stratiform and disseminated pyrite-arsenopyrite concentrations are overprinted by fracturecontrolled polymetallic mineralisation including stibnite through at least tens of metres of Silurian sediments at Glendinning, near Langholm. Three shallow boreholes were drilled on an anomaly defined by VLF-EM and II? surveys and by antimony values X0 ppm in thin B-C horizon soils. A parallel conductive zone with an accompanying soil anomaly but lacking an IP response was investigated by a fourth hole. The stratabound sulphides form disseminations and bands parallel to the bedding and are particularly concentrated in intraformational breccia units regarded as debris flows, which, together with the presence of smaIl scale slump folds in the greywackes, testify to the existence of an unstable slope during sedimentation. The thickest such unit has a true thickness of 4 m and together with 8 m of adjoining greywackes grades 0.7% As. Phases of fracture-controlled Fe-As-Sb-Pb- Zn-Cu-(?)Hg mineralisation associated with widespread dolomite and quartz veinlets and narrow breccia veins are superimposed on the stratabound mineralisation. Their spatial association with the stratabound mineralisation, the presence of up to 0.33% Sb in the stratiform arsenopyrite and as much as 5% As in the stratiform pyrite, favour a common source for the arsenic and antimony. This source was probably a synsedimentary metal accumulation in a mid or lower fan environment where euxinic conditions periodically developed