Chloride Brine Research Articles

In-situ X-ray absorption study of Iron(II) speciation in brines up to supercritical conditions

X-ray absorption spectroscopy (XAS) measurements were used to determine the coordination structure and to derive the speciation of aqueous ferrous chloride complexes in acidic chloride brines over a wide range of conditions (25–450 °C, 500 bar, 0.5–12 m chloride molality), covering the range from sedimentary brines to magmatic hydrothermal fluids. EXAFS analysis coupled with ab initio free potential XANES calculations confirmed the octahedral geometry of the different Fe chlorocomplexes at low temperature (< 200 °C) and low (< 1 m) chloride concentration ([FeCl x (H 2O) 6 − x ] 2 − x , x = 0–2), and attest the stability of a high-order tetrahedral Fe(II)-chloride complex at high-temperature (> 300 °C) and high (> 2 m) chloride molality ([FeCl y ] 2 − y ; y = 4 or y = 3; Fe–Cl distance = 2.31 ± 0.01 Å). These spectroscopic results contrast with the interpretation of most recent high-temperature studies of Fe(II) speciation in brines, which assumed that [FeCl 2] 0 is the predominant species in brines at high temperature. A reinterpretation of the experimental Fe solubilities measured by Fein et al. [Fein, J.B., Hemley, J.J., D'Angelo, W.M., Komninou, A., Sverjensky, D.A., 1992. Experimental study of iron-chloride complexing in hydrothermal fluids. Geochim. Cosmochim. Acta 56, 3179–3190.] for the magnetite–pyrite–pyrrhotite–quartz–muscovite–K-feldspar assemblage in KCl solutions at 300 °C/500 bar and 400 °C/500 bar shows that these solubility data can be explained using the high-order [FeCl 4] 2− complex. This study illustrates the complementarity between solubility and spectroscopic studies, and provides further evidence of the importance of high-order chlorocomplexes for the transport of transition metals (e.g., Zn, Ni) in high-temperature and/or supercritical fluids.

Slope streaks on Mars: A new “wet” mechanism

Slope steaks are one of the most intriguing modern phenomena observed on Mars. They have been mostly interpreted as some specific type of granular flow. We propose another mechanism for slope streak formation on Mars. It involves natural seasonal formation of a modest amount of highly concentrated chloride brines within a seasonal thermal skin, and runaway propagation of percolation fronts. Given the current state of knowledge of temperature regimes and the composition and structure of the surface layer in the slope streak regions, this mechanism is consistent with the observational constraints; it requires an assumption that a significant part of the observed chlorine to be in form of calcium and ferric chloride, and a small part of the observed hydrogen to be in form of water ice. This “wet” mechanism has a number of appealing advantages in comparison to the widely accepted “dry” granular flow mechanism. Potential tests for the “wet” mechanism include better modeling of the temperature regime and observations of the seasonality of streak formation.

Concentrated sodium chloride brine solutions as an additional treatment for preventing the introduction of nonindigenous species in the ballast tanks of ships declaring no ballast on board

Currently, seawater flushing is the only management strategy for reducing the number of viable organisms in residual sediments and water of ballast tanks of vessels declaring no ballast on board (NOBOB) that traffic ports of the eastern United States. Previously, we identified several species of freshwater and brackish-water peracarid crustaceans able to survive the osmotic shock that occurs during open-ocean ballast water exchange and, potentially, to disperse over long distances via ballasted ships and NOBOB vessels. We tested the efficacy of concentrated sodium chloride brine solutions as an additional treatment for eradicating the halotolerant taxa often present in the ballast tanks of NOBOB ships. The lowest brine treatments (30 ppt for 1 h) caused 100% mortality in several species of cladocerans and copepods collected from oligohaline habitats. Several brackish-water peracarid crustaceans, however, including some that can survive in freshwater as well, required higher brine concentrations and longer exposure durations (45-60 ppt for 3-24 h). The most resilient animals were widely introduced peracarid crustaceans that generally prefer mesohaline habitats but do not tolerate freshwater (required brine treatments of 60-110 ppt for 3-24 h). Brine treatments (30 ppt) also required less time to cause 100% mortality for eight taxa compared with treatments using 34 ppt seawater. Based on these experiments and published data, we present treatment strategies for the ballast tank biota often associated with NOBOB vessels entering the Great Lakes region. We estimate the lethal dosage of brine for 95% of the species in our experiments to be 110 ppt (95% confidence interval, 85-192 ppt) when the exposure time is 1 h and 60 ppt (95% confidence interval, 48-98 ppt) when the exposure duration is 6 h or longer.

Naturally acid waters from Copahue volcano, Argentina

Volcanic acid sulfate–chloride brines form through absorption of volcanic vapors in shallow reservoirs of meteoric water. Reaction with surrounding volcanic rocks leads to partial neutralization of the fluids and precipitation of secondary minerals. Chemical data of such acid waters from Copahue volcano, Argentina, covering 8 years of observations, show evidence for changes in composition related to water rock interaction at depth prior to emergence of the fluids at the surface. The chemical composition changed dramatically during the 2000 eruption of Copahue, with enhanced concentrations and fluxes of Mg, Na, Fe and Al, followed in 2001 by rapidly declining concentrations and element fluxes. The subsequent 5 years saw more variable element ratios and strong depletions in K and Al. Most incompatible elements are released from the rock matrix stochiometrically, whereas some elements are enriched through vapor input from the magma (As, Pb, Zn). Most fluids have LREE enrichments relative to the rock matrix, but during periods of new magma intrusion the LREE enrichment decreases as does the magnitude of the negative Eu anomaly in the fluids. These observations are interpreted assuming early dissolution of plagioclase, olivine and volcanic glass that occurs during intrusion of new magma into the hydrothermal system. The high field strength elements are virtually immobile even in these hot acid fluids, with Nb and Ta more so than Hf and Zr. The mobility of U and Th in these fluids is comparable, at variance with Th behavior in neutral fluids. The local rivers and lakes of Copahue are fertilized by volcanic dissolved P, and most surface waters with pH < 3 have high levels of As. The acid fluids from Copahue may be surficial analogs for deep subduction fluids that evolve below zones of arc magma generation as well as for early Mars environments that are thought to have had large acid lakes.

Application of an ultrasonic assisted curing technique for improving the diffusion of sodium chloride in porcine meat

Pork loins ( Longissimus dorsi) were immersed in sodium chloride brine (40 g L −1) and treated at 5 °C with one of the three following brining treatments: (1) static brining, (2) vacuum tumbling, or (3) ultrasonic brining at low-frequency (20 kHz) and low-intensity (2–4 W cm −2). The effect of ultrasonic and tumbling assisted curing technology on porcine tissue microstructure, protein denaturation, water-binding capacity (WBC), water-holding capacity (WHC), sodium chloride diffusion coefficient ( D) and on meat textural profile (TPA) was investigated. Results showed that both ultrasonic treatment and tumbling caused favourable microstructural changes in meat tissue. Water-holding capacity and textural properties were improved by ultrasonic treatment compared to both tumbled and static brined samples. However, these positive effects were highly dependent on ultrasonic intensity. Higher intensities and/or longer treatment times caused denaturation of proteins. The constant diffusion coefficient model was able to describe precisely the NaCl diffusion kinetics during brining. Ultrasonic treatment significantly enhanced the diffusion of salt compared to samples brined under static conditions and diffusion coefficient exponentially increased with increased ultrasonic intensity.

Operational Data From the World's First SAGD Facilities Using Evaporators to Treat Produced Water for Boiler Feedwater

Abstract Many new Steam-Assisted Gravity Drainage (SAGD) heavy oil recovery facilities have recently shifted from the use of warm or hot lime softening, filtration and weak acid cation (WAC) ion exchange to pretreat de-oiled produced water to an approach using falling film, mechanical vapour recompression evaporation to produce steam generator feedwater. This method of SAGD-produced water treatment is much simpler to operate, is more cost effective and results in significant increases in equipment reliability, on-stream availability and, ultimately, oil production. There are currently about 14 such evaporators operating, under construction, or in various stages of delivery in Alberta and overseas. Several of these evaporators produce feedwater for standard drum-type boilers rather than the traditional Once-Through Steam Generators (OTSG) due to the high level of water purity obtainable with the evaporative approach. This paper provides data from operational facilities, including evaporator distillate quality, heat transfer information, fouling rates, cleaning frequencies, energy and chemical consumption, and other technical and operational data. In conjunction with this evaporative produced water treatment process, some facilities have taken the additional step of recovering all liquid waste streams for re-use in the plant, resulting in zero liquid discharge (ZLD). Designing the facility for ZLD eliminates the need for deep well injection, minimizes make-up water requirements and simplifies the permitting process. Introduction The recovery of heavy oil from oil sands formations requires large volumes of water; sometimes three times the amount of water compared to the oil recovered. In steam-assisted gravity drainage (SAGD) facilities, 100% quality steam is injected into the well to heat up the formation and get the heavy oil to flow. Oil and condensed steam are brought to the surface where the oil is separated and the condensate, or produced water, is treated and recycled to produce the steam. This huge water demand and ultimate conversion to steam requires the maximum amount of recycle potential from the water. Produced water derived from oil recovery processes (SAGD and non-SAGD) can be characterized as predominantly sodium chloride brine with high silica and minimal amounts of hardness. High alkalinity is present as well. Overall concentration of the water can range from about 1,000 mg per litre TDS to over 10,000 mg per litre, and there is always some amount of organic material present. The method of converting this water to boiler feedwater must be carefully evaluated, both technically and economically. This paper discusses an evaporative method of deriving high quality boiler feedwater from produced water. A comparison is made to the 'traditional' method of warm (or hot) lime softening combined with weak acid cation exchange (WLS/WAC). A complete evaluation of these two approaches must also include the steam generation equipment. Having high quality boiler feedwater, as derived from an evaporative process, allows the use of drum boilers in lieu of once-through steam generators (OTSG). Since the WLS/WAC system does not produce a high quality water, OTSG must be used as these boilers are more tolerant of poorer quality feedwater.

Fracture Acidizing: What Role Does Formation Softening Play in Production Response?

Summary Fracture acidizing of carbonates has yielded increases in production in many areas of the world, but depending on rock strength and reservoir closure pressure, this response may be lower than expected. Also, as a result of rock strength and closure pressure, production may decline at a higher rate than following a proppant fracture treatment. Laboratory results are presented describing the effect of various acid systems on the strength reduction of limestone and dolomite-formation rock samples. Formation samples were dry or saturated with 2-wt% potassium chloride brine before testing. Samples were exposed to neat, emulsified, gelled, and crosslinked 15-wt% hydrochloric acids (HCl) and each exhibited a differing effect on rock-strength reduction. In addition, production responses are presented and compared with regard to the type of acid system used for stimulation. On the basis of the results obtained, acid-system choices made a significant difference in the degree of rock softening of carbonates. Emulsified acid caused the least softening effect on limestone and dolomite cores. Softening effects were greater on limestone than on dolomite rocks. Production responses from emulsified-acid treatments were best.

Concentration of pineapple juice by osmotic evaporation

The aim of this work was to evaluate the process of osmotic evaporation to concentrate pineapple juice. In order to study the effect of pulp content on the performance, clarified and single strength pineapple juices were successively concentrated up to 57g100g−1 total soluble solids (TSS). Trials were carried out with a laboratory unit using saturated calcium chloride brine as the extracting phase. Under the operating conditions, the difference in temperature between the juice and the brine had a large influence on the water evaporation rate. The highest flux was obtained at 35°C in the juice compartment and 20°C on the brine side. Flux ranged from 2 to 13kgh−1m−2. It significantly decreased when the TSS content of the juice increased. For the same operating conditions, higher flux values were obtained when processing the clarified juice, which indicated an effect of pulp content on performance. At no time were significant changes observed in the quality of the products obtained from raw juices and juices from concentrates.

RECOVERY OF COPPER FROMAMASSIVE POLYMETALLIC SULPHIDE BY HIGH CONCENTRATION CHLORIDE LEACHING

A new process for the recovery of copper and associated base metals from a polymetallic massive sulphide ore is described. The massive sulphide contains copper and especially nickel sulphide in a mineralogical form which negates both good recovery and high grades in concentrates using conventional flotation methods. Utilizing the properties of high concentration chloride brines, a hydrometallurgical flowsheet has been developed and tested whereby the recovery of all of the metals and some of the power requirements for the plant itself can be derived from the ore. The new process involves leaching of the whole ore in two stages: 1) a primary leach during which the pyrrhotite is leached with HCl assisted by MgCl2 to yield hydrogen sulphide (from which energy is produced) and 2) a ferrous chloride solution; a secondary ferric chloride/MgCl2 oxidizing leach during which the economic metals (C, Ni and Co) are solubilized. The generated primary ferrous chloride leach solution is subjected to oxidation and hydrolytic decomposition to precipitate the excess iron as hematite and regenerate the HCl lixiviant. Copper recovery is effected via ion exchange and generation of a copper sulphate electrolyte advanced to conventional electrowinning. The Ferguson Lake deposit of Starfield Resources Inc. in Nunavut, Canada, is the subject of this paper, which focuses on the leaching and copper recovery unit operations of the proposed flowsheet.On decrit un nouveau procede pour la recuperation du cuivre et des metaux de base associes d’un minerai polymetallique massif de sulfure. Le sulfure massif contient du cuivre et surtout du sulfure de nickel sous une forme mineralogique qui empeche a la fois une bonne recuperation et des teneurs elevees dans les concentres lorsqu’on utilise les methodes conventionnelles de flottation. Utilisant les proprietes de saumures de chlorure a concentration elevee, on a developpe et evalue un schema de procede d’hydrometallurgie par lequel on peut deriver, a partir du minerai, la recuperation de tous les metaux et une partie de l’energie necessaire pour l’usine meme. Le nouveau procede implique la lixiviation du minerai entier en deux etapes: 1) un lessivage primaire durant lequel la pyrrhotine est lessivee avec du HCl assiste deMgCl2 pour produire de l’acide hydrosulfurique (a partir duquel on produit de l’energie) et 2) une solution de chlorure ferreux; un lessivage oxydant secondaire de chlorure ferrique/MgCl2 lors duquel on solubilise les metaux economiques (C, Ni et Co). La solution de lessivage primaire generee de chlorure ferreux est soumise a une oxydation et une decomposition hydrolytique pour precipiter l’exces de fer en hematite et pour regenerer le lixiviat HCl. La recuperation du cuivre est effectuee via l’echange d’ions et la production d’un electrolyte de sulfate de cuivre, avancee a l’electro-obtention conventionnelle. Le depot de Ferguson Lake de Starfield Resources Inc. au Nunavut, Canada, est le sujet de cet article, lequel se concentre sur les unites d’operation de lixiviation et de recuperation du cuivre du schema de procede propose.

Thermodynamic model of natural brines accounting for the presence of trace components: II. System Na+, K+, Mg2+ ‖ Cl−, Br−-H2O

This paper reports the calculations of parameters for the Pitzer equation and thermodynamic potentials of solid phases crystallizing in water-salt systems modeling chloride brines taking into account the presence of bromide ions in them. Solubility diagrams were calculated for corresponding ternary and quaternary systems containing chlorides and bromides of sodium, potassium, and magnesium at 25°C. The results of calculations are in adequate agreement with the available published experimental data on solubility and can be used to model salt crystallization during the concentration of seawater and brines.

Manufacturing of magnesium hydroxide from natural magnesium chloride sources

Various processes for manufacturing magnesium hydroxide have been considered and tested in order to decide whether they can be employed to the full-scale production of this product from natural sources (bischofite and magnesium chloride brines). The process for the synthesis of magnesium hydroxide from magnesium chloride using sodium hydroxide has been improved.

Corrosion Resistances of Iron-Based Amorphous Metals with Yttrium and Tungsten Additions in Hot Calcium Chloride Brine & Natural Seawater: Fe48Mo14Cr15Y2C15B6 and W-Containing Variants

Yttrium-containing SAM1651 (Fe48.0Cr15.0Mo14.0B6.0C15.0Y2.0), has a critical cooling rate (CCR) of approximately 80 Kelvin per second, while SAM2X5 (Fe49.7Cr17.7Mn1.9Mo7.4W1.6B15.2C3.8Si2.4) with no yttrium has a higher critical cooling rate of approximately 600 Kelvin per second. SAM1651's low CCR enables it to be rendered as a completely amorphous material in practical materials processes. Chromium (Cr), molybdenum (Mo) and tungsten (W) provide corrosion resistance; boron (B) enables glass formation; and rare earths such as yttrium (Y) lower critical cooling rate (CCR). The passive film stability of these Fe- based amorphous metal formulations have been found to be superior to that of conventional stainless steels, and comparable to that of Ni-based alloys, based on electrochemical measurements of the passive film breakdown potential and general corrosion rates.

The Effect of Anions on the Passive Film Properties and Localized Corrosion Behavior of Alloy C-22

This paper investigates corrosion behavior of Alloy C-22 in hot concentrated brines. The passive film behavior and localized corrosion properties of alloy C-22 as a function of nitrate and sulfate anions in concentrated chloride brines was investigated. Cyclic potentiodynamic polarization tests were used to study the general corrosion behavior of the alloy, Electrochemical Impedance Spectroscopy (EIS) and Mott-Schottky (M-S) were used to examine the electronic properties of the passive films, and constant potential tests were done to study crevice corrosion initiation, propagation and stifling of the alloy. The aim was to investigate the correlation between the electronic properties of the alloy's passive film and the localized corrosion susceptibility of the alloy. The results showed that anions had major impact on the repair- repassivation behavior but did not cause significant effect on the properties of passive film when it was intact.

Ultrasonic degradation of metal complexes with organic substances present in mineralized water, brines, and sodium chloride solutions

The applicability of ultrasound over a frequency range from 18 kHz to 2 MHz to the degradation of metal complexes with organic compounds present in water, brines, and sodium chloride solutions was studied. It was found that ultrasound over a frequency range from 18 to 100 or 200 kHz can be used for the degradation of complexes in sodium chloride solutions and brines or seawater, respectively. In this case, the best results were obtained over the frequency range 80–100 or 80–200 kHz, respectively.

Prediction of Strontium Sulfate Scale Formation in Oilfield Environment

Abstract An easy and reliable method for predicting a scale tendency of strontium sulfate as a function of several variables including sodium chloride brine composition, temperature, and pressure effect is developed. The effect of the amount of sulfate tied up as [MgSO40] on SrSO4 solubility is also considered. The magnesium sulfate dissociation constants and strontium sulfate experimental solubility data is fitted in mathematical equations. These equations can be easily used to determine SrSO4 scaling tendency in environments common to oil field brines. The reliability and key features of the prediction method are illustrated in the text with oilfield well cases. Results obtained using the present model are in good agreement with field observation. The method presented in this study is easy to use, reliable, and can be applied to any producing wells where SrSO4 occurs.

Isotopic composition (H, O, Cl, Sr) of ground brines of the Siberian Platform

New data on the geochemistry and isotopic composition of chloride brines of the Siberian Platform are presented. The distribution of stable isotopes ( 2H, 18O, and 37Cl) in brines of the Tunguska, Angara-Lena, western part of the Yakutian and Olenek artesian basins and 87Sr/ 86Sr in brines of the western part of the Olenek artesian basin was studied in the context of the problem of genesis of highly mineralized groundwaters. Results of the study and comparative analysis of the geochemical and isotopic peculiarities of the Siberian Platform brines conform to the theory of brine formation through the interaction of connate waters with enclosing rocks.

Determination of calcium chloride brine concentration required to provide pressure overbalance

In this study we present an equation of state (pressure–density–temperature dependence) for calcium chloride brine. The empirical coefficients in this equation are expressed as functions of the brine weight concentration ( W). Thus for an actual temperature profile and specified downhole pressure the needed brine concentration can be determined. Knowledge of pressure exerted by a brine as function of downhole temperature, vertical depth, and brine concentration in HPHT wells will allow one to control the overbalance levels.

Glauberite–halite association of the Zaragoza Gypsum Formation (Lower Miocene, Ebro Basin, NE Spain)

AbstractGlauberite is the most common mineral in the ancient sodium sulphate deposits in the Mediterranean region, although its origin, primary or diagenetic, continues to be a matter of debate. A number of glauberite deposits of Oligocene–Miocene age in Spain display facies characteristics of sedimentologic significance, in particular those in which a glauberite–halite association is predominant. In this context, a log study of four boreholes in the Zaragoza Gypsum Formation (Lower Miocene, Ebro Basin, NE Spain) was carried out. Two glauberite–halite lithofacies associations, A and B, are distinguished: association (A) is composed of bedded cloudy halite and minor amounts of massive and clastic glauberite; association (B) is made up of laminated to thin‐bedded, clear macrocrystalline, massive, clastic and contorted lithofacies of glauberite, and small amounts of bedded cloudy halite. Transparent glauberite cemented by clear halite as well as normal‐graded and reverse‐graded glauberite textures are common. This type of transparent glauberite is interpreted as a primary, subaqueous precipitate. Gypsum, thenardite or mirabilite are absent in the two associations. The depositional environment is interpreted as a shallow perennial saline lake system, in which chloride brines (association A) and sulphate–(chloride) brines (association B) are developed. The geochemical study of halite crystals (bromine contents and fluid inclusion compositions) demonstrates that conditions for co‐precipitation of halite and glauberite, or for precipitation of Na‐sulphates (mirabilite, thenardite) were never fulfilled in the saline lake system.

Corrosion Resistances of Iron-Based Amorphous Metals with Yttrium and Tungsten Additions in Hot Calcium Chloride Brine

not Available.

Hydrodynamic and geochemical conditions of the formation of stratiform Zn-Pb ore mineralization by chloride solutions

Ore mineralization is formed by postsedimentary (concentrated by evaporation to stage SW2) chloride brines metamorphosed in hydrogeochemical systems that are closed with respect to CO2, evolve according to “calcic” trend, and have high 2mCa2+ > mHCO 3 − + 2mCO 3 2− ratios. In these situations at high R/W ratios (10–100) and temperatures (100–200°C), these brines concentrate ore elements (Zn, Pb, Fe, and Mn) that are geochemical analogues of Ca. The sulfide precipitation of these elements occurs under the effect of carbonate rocks at the abiogenic sulfate reduction of S(VI) of the original brines at low Eh values, which are created in carbonate rocks at higher (>100°C) temperatures. This origin of sulfide mineralization is intensified at decreasing R/W ratios during the dilution of the original brines by elision waters and an increase in the temperature. The hydrodynamics of these ore-forming brines is controlled by the elision hydrogeological regime, which is defined in hydrogeological structures by the geostatic pressure. The brines migrate into the zones of geochemical barriers during the relaxation of hydrogeological structures toward their equilibrium hydrostatic state. Hydrogeological structures, optimal for the precipitation of ore mineralization, are hydrodynamically active and able to maintain a steady (during 105-106 years) inflow of ore-forming brines into the zones of geochemical barriers and the maximum number of water-exchange cycles at these barriers. Modern analogues of these structures are miogeosyncline foredeeps with Cl-Na-Ca chloride brines with high concentrations of ore elements and overall flow rates ranging from 0.n to n m3/year. Stagnate hydrogeological platform structures in hydrostatic equilibrium cannot ensure water exchange needed for ore formation, and, hence, the brines of these structures are not able to deposit the ore elements contained in them, in spite of the high concentrations of these elements.