Michal Filippi

Secondary arsenic minerals in the environment: A review

Information on arsenic (As) speciation in solid materials is critical for many environmental studies concerned with As stability and/or mobility in natural As-impacted soils and mining or industrial sites contaminated by As. The investigation of these systems has provided evidence for a number of secondary As minerals that have often played a significant role in As mobility in the solid phase-water system. This paper presents a list of environmentally important secondary As minerals in contaminated soil and waste systems, summarizes the information about their origin, occurrence, environmental stability and thermodynamics, and proposes several important avenues for further investigation.

Mineralogical and geochemical controls of arsenic speciation and mobility under different redox conditions in soil, sediment and water at the Mokrsko-West gold deposit, Czech Republic

Naturally contaminated soil, sediment and water at the Mokrsko-West gold deposit, Central Bohemia, have been studied in order to determine the processes that lead to release of As into water and to control its speciation under various redox conditions. In soils, As is bonded mainly to secondary arseniosiderite, pharmacosiderite and Fe oxyhydroxides and, rarely, to scorodite; in sediments, As is bonded mainly to Fe oxyhydroxides and rarely to arsenate minerals. The highest concentrations of dissolved As were found in groundwater (up to 1141 microg L(-1)), which mostly represented a redox transition zone where neither sulphide minerals nor Fe oxyhydroxide are stable. The main processes releasing dissolved As in this zone are attributed to the reductive dissolution of Fe oxyhydroxides and arsenate minerals, resulting in a substantial decrease in their amounts below the groundwater level. Some shallow subsurface environments with high organic matter contents were characterized by reducing conditions that indicated a relatively high amount of S(-2,0) in the solid phase and a lower dissolved As concentration (70-80 microg L(-1)) in the pore water. These findings are attributed to the formation of Fe(II) sulphides with the sorbed As. Under oxidizing conditions, surface waters were undersaturated with respect to arsenate minerals and this promoted the dissolution of secondary arsenates and increased the As concentrations in the water to characteristic values from 300 to 450 microg L(-1) in the stream and fishpond waters. The levels of dissolved As(III) often predominate over As(V) levels, both in groundwaters and in surface waters. The As(III)/As(V) ratio is closely related to the DOC concentration and this could support the assumption of a key role of microbial processes in transformations of aqueous As species as well as in the mobility of As.

Raman Microspectroscopy as a Valuable Additional Method to X-ray Diffraction and Electron Microscope/Microprobe Analysis in the Study of Iron Arsenates in Environmental Samples

In this paper, we demonstrate that combined application of X-ray diffraction (XRD), electron microscope/microprobe analysis (EMPA), and Raman microspectroscopy is an available and powerful approach for identification and characterization of iron arsenate minerals in complex environmental samples. Arsenic-rich material from the medieval mining dump close to the Giftkies mine in the Jáchymov ore district (Czech Republic) has been studied. Scorodite, kaňkite, amorphous iron arsenate (pitticite), and, to a lesser extent, native sulfur were determined in the studied samples as products of low-temperature arsenopyrite weathering. Scorodite and kaňkite form mixed nodules and crusts, which are locally coated by hardened gel-like amorphous pitticite. Pitticite also borders fractures in the mineralized rock fragments in the dump. Native sulfur, in microscopic crystals and grainy aggregates, originates directly in places with dissolved arsenopyrite and forms pseudomorphs. The Raman spectra presented in the paper can serve as comparative data for phase identification in other contaminated areas. New Raman data for the hydroxyl stretching region of scorodite (important bands: 3514, 3427, and 3600 cm−1) and the whole Raman spectrum for pitticite (important bands: 472, 831, 884, 2935, 3091, 3213, 3400, and 3533 cm−1) are a valuable output of this paper.

Natural attenuation of arsenic in soils near a highly contaminated historical mine waste dump

Arsenic-contaminated soils near historical As-rich mine waste in Jáchymov (Czech Rep.), resulting from the smelting and seepage of the mine waste pore water, were studied to examine As partitioning between solid phases and pore waters. Mineralogical and geochemical analyses showed that As is exclusively associated with unidentified amorphous Fe oxyhydroxides, poorly crystalline goethite and hematite as adsorbed and coprecipitated species (with up to 3.2 wt.% As). Adsorption of As by Fe oxyhydroxides is likely to be a major control on the migration of As in the soil pore water containing only up to 15 μg L(-1) As(V). The slight variations in the dissolved As(V) concentrations do not follow the total contents of As in the soil or adsorbed As, but appeared to be a function of pH-dependent sorption onto Fe oxyhydroxides. The geochemical modelling using PHREEQC-2 supported the efficiency of As(V) adsorption by Fe oxyhydroxides in the soil affected by As-rich waste solution seepage. It also suggested that active Fe oxyhydroxides has a strong attenuation capacity in soil that could effectively trap the aqueous As(V) from the unremitting waste seepage for the next approx. 11600 years.

Secondary halite deposits in the Iranian salt karst: general description and origin

This paper summaries 12 years of documentation of secondary halite deposits in the Iranian salt karst. A variety of secondary halite deposits was distinguished and classified into several groups, on the basis of the site and mechanism of their origin. Deposits formed: i) via crystallization in/on streams and pools, ii) from dripping, splashing and aerosol water, iii) from evaporation of seepage and capillary water, and iv) other types of deposits. The following examples of halite forms were distinguished in each of the above mentioned group: i) euhedral crystals, floating rafts (raft cones), thin brine surface crusts and films; ii) straw stalactites, macrocrystalline skeletal and hyaline deposits, aerosol deposits; iii) microcrystalline forms (crusts, stalactites and stalagmites, helictites); iv) macrocrystalline helictites, halite bottom fibers and spiders, crystals in fluvial sediments, euhedral halite crystals in rock salt, combined or transient forms and biologically induced deposits. The occurrence of particular forms depends strongly on the environment, especially on the type of brine occurrence (pool, drip, splashing brine, microscopic capillary brine, etc.), flow rate and its variation, atmospheric humidity, evaporation rate and, in some cases, on the air flow direction. Combined or transitional secondary deposits can be observed if the conditions changed during the deposition. Euhedral halite crystals originate solely below the brine surface of supersaturated streams and lakes. Macrocrystalline skeletal deposits occur at places with rich irregular dripping and splashing (i.e., waterfalls, places with strong dripping from the cave ceilings, etc.). Microcrystalline (fine grained) deposits are generated by evaporation of capillary brine at places where brine is not present in a macroscopically visible form. Straw stalactites form at places where dripping is concentrated in small spots and is frequent sufficient to assure that the tip of the stalactite will not be overgrown by halite precipitates. If the tip is blocked by halite precipitates, the brine remaining in the straw will seep through the walls and helictites start to grow in some places. Macrocrystalline skeletal deposits and straw stalactites usually grow after a major rain event when dripping is strong, while microcrystalline speleothems are formed continuously during much longer periods and ultimately (usually) overgrow the other types of speleothems during dry periods. The rate of secondary halite deposition is much faster compared to the carbonate karst. Some forms increase more than 0.5 m during the first year after a strong rain event; however, the age of speleothems is difficult to estimate, as they are often combinations of segments of various ages and growth periods alternate with long intervals of inactivity. Described forms may be considered in many cases as the analogues of forms found in the carbonate karst. As they are created in a short time period the conditions of their origin are often still visible or can be reconstructed. The described halite forms can thus be used for verification of the origin of various carbonate forms. Some of the described forms bear clear evidence of the paleo-water surface level (transition of the skeletal form to halite crystals and vice versa). Other kinds of deposits are potential indicators of the microclimate under which they developed (humidity close to the deliquescence relative humidity).

Arsenic mineralogy and mobility in the arsenic-rich historical mine waste dump.

A more than 250 year-old mine dump was studied to document the products of long-term arsenopyrite oxidation under natural conditions in a coarse-grained mine waste dump and to evaluate the environmental hazards associated with this material. Using complementary mineralogical and chemical approaches (SEM/EDS/WDS, XRD, micro-Raman spectroscopy, pore water analysis, chemical extraction techniques and thermodynamic PHREEQC-2 modeling), we documented the mineralogical/geochemical characteristics of the dumped arsenopyrite-rich material and environmental stability of the newly formed secondary minerals. A distinct mineralogical zonation was found (listed based on the distance from the decomposed arsenopyrite): scorodite (locally associated with native sulfur pseudomorphs) plus amorphous ferric arsenate (AFA/pitticite), kaňkite, As-bearing ferric (hydr)oxides and jarosite. Ferric arsenates and ferric (hydr)oxides were found to dissolve and again precipitate from downward migrating As-rich solutions cementing rock fragments. Acidic pore water (pH3.8) has elevated concentrations of As with an average value of about 2.9 mg L(-1). Aqueous As is highly correlated with pH (R2=0.97, p<0.001) indicating that incongruent dissolution of ferric arsenates controls dissolved As well as the pH of the percolating waste solution. Arsenic released from the dissolution of ferric arsenates into the pore water is, however, trapped by latter and lower-down precipitating jarosite and especially ferric (hydr)oxides. The efficiency of As sequestration by ferric (hydr)oxides in the waste dump and underlying soil has been found to be very effective, suggesting limited environmental impact of the mine waste dump on the surrounding soil ecosystems.

Quantitative study of a rapidly weathering overhang developed in an artificially wetted sandstone cliff

Those factors controlling the weathering and erosion of sandstone on the field scale are still not well understood. In this study, a specific sandstone overhang (and its surroundings) with artificially induced and extremely high erosion rates was subjected to a complex investigation. Contrast between the erosion rate of the wet and dry portions of the same cliff enabled isolation of the factors responsible for rapid sandstone retreat. Erosion rates, moisture, and salt content, as well as suction were monitored in the field. Mineral phases and water chemistry were analyzed. The measurement of tensile strength, laboratory frost weathering tests, and numerical modeling of stress were performed. The acquired data show that an increase of moisture content in pores in the area of the studied overhang decreased tensile strength of the sandstone to 14 % of its dry value, and increases the sandstone weathering and erosion rate, by nearly 4 orders of magnitude, compared to the same sandstone under natural moisture condition outside on the cliff area. Consequently, frost weathering, in combination with wetting weakening was found to play a major role in weathering/erosion of the sandstone cliff and overhang. Frost weathering rate in both the laboratory and field increases up to 15 times with decreasing gravity-induced stress. The results also indicate that sandstone landforms in temperate climates may potentially develop very rapidly if the pore space is nearly saturated with water, and will later remain relatively stable when the moisture content decreases. As a general implication, it is suggested that overhangs in Central Europe (and elsewhere) might be the result of rapid frost weathering of nearly saturated sandstone during the Last Glacial. This article is protected by copyright. All rights reserved.

Cryogenic Mineral Formation in Caves

Abstract Freezing of karst water in caves forces the segregation of solutes, a process of rejection of dissolved ions by the advancing ice-water front during the growth of ice crystals. This process causes supersaturation of the unfrozen residual part of the solution and precipitation of some of dissolved compounds as minerals. Water evaporation and solution degassing additionally enhance the mineral formation. The cryogenic cave minerals constitute a variety of speleothems, which differ in practically all aspects from their counterparts formed in caves unaffected by freezing. The morphology and mineralogy of cryogenic cave minerals largely depend on the initial chemical composition of the karst water, the thickness of the water layer that freezes, and the freezing rate. The most common cryogenic minerals in the ice caves of limestone karst are fine-grained (powdery) carbonates produced by rapid water freezing in thin water layers. In contrast, slower freezing of large water volumes at cave temperature near 0°C produces coarse-grained cryogenic cave carbonates, which are typically associated with present or past permafrost conditions. Overall, the cryogenic cave carbonates are characterized by C and O isotope signatures different from that of speleothems in temperate environments. Apart from the cryogenic carbonates, several other freeze-related minerals have been identified in caves. By far, the richest diversity of cryogenic minerals occurs in gypsum-hosted ice caves.

Jahani Salt Diapir, Iran: hydrogeology, karst features and effect on surroundings environment

The Jahani Salt Diapir (JSD), with an area of 54 km(2), is an active diapir in the Simply Folded Belt of the Zagros Orogeny, in the south of Iran. Most of the available studies on this diapir are f ...

Hydrogeology of salt karst under different cap soils and climates (Persian Gulf and Zagros Mts., Iran)

*bruthans@natur.cuni.cz Citation: