Molecular Atomistic Simulations of Clay Swelling in Water Dispersions

An atomistic model has been constructed for a dimeric montmorillonite type clay aggregate. The solid was supposed to be dispersed in water. The surrounding aqueous phase was modified from pure water to either salt or polymer solution, and finally represented by a mixed solution containing electrolytes and polyols. A combined energy minimisation procedure followed by a 100 ps real time molecular dynamic simulation was performed on each amorphous cell modelling the solid dispersion. 3D periodic boundary conditions were established to ensure fluid spatial continuity and the calculations proceeded at room temperature. Sodium, potassium and calcium chlorides were tested as shale swelling inhibition additives. The lower hydration energy cation K⁺ was the most effective swelling inhibitor. The adsorption of poly(propylene glyco)s to the ideal smectite surface was also studied. Their tendency to remain adsorbed was associated with the irreversibility of the polymer adsorption process. The conformational changes obtained for organic molecules were responsible for the final orientation of the clay sheets. So it was possible to conclude from qualitative observations that intramolecular interactions may determine a clay dispersion–agglomeration transition by modifying the system entropy. Finally, it was also concluded that specific combinations of additives could enhance their individual capabilities by synergistic effects, determining the effectiveness for some water-based mud formulations. This revised version was published online in June 2006 with corrections to the Cover Date.     

Biodegradation of crude oil saturated fraction supported on clays

The role of clay minerals in crude oil saturated hydrocarbon removal during biodegradation was investigated in aqueous clay/saturated hydrocarbon microcosm experiments with a hydrocarbon degrading microorganism community. The clay minerals used for this study were montmorillonite, palygorskite, saponite and kaolinite. The clay mineral samples were treated with hydrochloric acid and didecyldimethylammonium bromide to produce acid activated- and organoclays respectively which were used in this study. The production of organoclay was restricted to only montmorillonite and saponite because of their relative high CEC. The study indicated that acid activated clays, organoclays and unmodified kaolinite, were inhibitory to biodegradation of the hydrocarbon saturates. Unmodified saponite was neutral to biodegradation of the hydrocarbon saturates. However, unmodified palygorskite and montmorillonite were stimulatory to biodegradation of the hydrocarbon saturated fraction and appears to do so as a result of the clays’ ability to provide high surface area for the accumulation of microbes and nutrients such that the nutrients were within the ‘vicinity’ of the microbes. Adsorption of the saturated hydrocarbons was not significant during biodegradation.     

The effect of clays on the oligomerization of HCN

Summary The reaction of 0.1 M HCN and dilute solutions of diaminomaleonitrile (DAMN) at pH 8–9 and 25°C in the presence of suspensions of montmorillonite (bentonite) clays were investigated. Montmorillonite clays inhibit the oligomerization of aqueous solutions of HCN. Yields of colored oligomers, urea, and DAMN, are all diminished by clays, but the rate of loss of cyanide is not significantly decreased. The inhibition of oligomer formation is due to the clay-catalyzed decomposition of DAMN. The absence of strong binding of DAMN to clays was suggested by our failure to detect DAMN when a clay that had been incubated with DAMN was washed with spermidine (6 × 10^–3 g/{ie317-1}). It was established that DAMN does not simply bind to the clays by the observation that the bulk of the radioactivity was recovered from the supernatant in the reaction of¹⁴C-DAMN with montmorillonite. The clay-catalyzed decomposition of DAMN was observed when montmorillonite from two different sources was used and with a variety of homoionic montmorillonites and bentonites. A modification of the established procedure for using the cyanide electrode for cyanide analyses was used to follow the release of HCN from DAMN. This new method can be used in both the acidic and basic pH range and it does not result in the destruction of DAMN by the reagents used for the analysis. Quantitative analyses of the reaction solution from the clay-catalyzed decomposition of DAMN revealed the formation of 1–2 equivalents of HCN per mole of DAMN. The possible significance of these clay-catalyzed reactions in chemical evolution is discussed. Chemical Evolution 35: For the previous papers in this series see Ferris, J P. and Joshi, P.C., (1978), Science 201, 361–362; Ferris, J.P., Narang, R.S., Newton, T.A. and Rao, V.R., (1979), J. Org. Chem. 44, 1273–1278; Ferris, J.P. (1979), Science 203, 1135–1136; Ferris, J.P. and Joshi, P.C., (1979), J. Org. Chem. 44, 2133–2137     

Slow vapor‐phase desorption of toluene from several ion‐exchanged montmorillonites

The sorption and desorption of volatile compounds from soils and clays exhibit a wide range of kinetics. While much of the sorptive interaction is very rapid, a certain fraction of volatile compounds that enter soil and clays are only slowly desorbed. It is generally believed that the formation of this recalcitrant or slowly desorbing fraction of volatile organic compounds (VOCs) in soils is due to the diffusion of compounds to poorly accessible sorption sites. However, the exact nature of these sites is in doubt. In montmorillonite, there are two likely possibilities for formation of the recalcitrant fraction: sites between the clay lamella and sites within clay particle aggregates. Because montmorillonite may be an important fraction of many soils, we have explored the formation of slowly desorbing toluene on a montmorillonite clay that was ion exchanged with five different ions (K⁺, Na⁺, Ca²⁺, Mg²⁺, and Fe³⁺) to form mineralogically similar clays with varying interlamellar spacing. The recalcitrant fraction was quantified for varying sorption and desorption times. The type of ion exchanged into the clay appears to have an important influence on the formation of a recalcitrant fraction.     

Insecticidal Activity of the Toxins from Bacillus thuringiensis subspecies kurstaki and tenebrionis Adsorbed and Bound on Pure and Soil Clays

The release of transgenic plants and microorganisms expressing truncated genes from various subspecies of Bacillus thuringiensis that encode active insecticidal toxins rather than inactive protoxins could result in the accumulation of these active proteins in soil, especially when bound on clays and other soil particles. Toxins from B. thuringiensis subsp. kurstaki and B. thuringiensis subsp. tenebrionis, either free or adsorbed at equilibrium or bound on pure clay minerals (montmorillonite or kaolinite) or on the clay size fraction of soil, were toxic to larvae of the tobacco hornworm (Manduca sexta) and the Colorado potato beetle (Leptinotarsa decemlineata), respectively. The 50% lethal concentrations (LC(inf50)) of free toxins from B. thuringiensis subsp. kurstaki were higher than those of both bound and adsorbed complexes of these toxins with clays, indicating that adsorption and binding of these toxins on clays increase their toxicity in diet bioassays. The LC(inf50) of the toxin from B. thuringiensis subsp. tenebrionis that was either free or adsorbed on montmorillonite were comparable, whereas the toxin bound on this clay had higher LC(inf50) and the toxin bound on kaolinite had lower LC(inf50) than when adsorbed on this clay. Results obtained with the clay size fraction separated from unamended soil or soil amended with montmorillonite or kaolinite were similar to those obtained with the respective pure clay minerals. Therefore, insecticidal activity of these toxins is retained and sometimes enhanced by adsorption and binding on clays.     

Decaying in different clays: implications for soft‐tissue preservation

Lagerstätten, places where soft‐bodied organisms became mineralized, provide a substantial bulk of palaeobiological information, but the detailed mechanisms of how soft‐tissue preservation takes place remain debatable. An experimental taphonomy approach, which allows for direct study of decay and mineralization, offers a means to study the preservational potential of different soft‐bodied organisms under controlled conditions. Here we compare the preservational capacity of two types of clay (kaolinite and montmorillonite) through a long‐term (24 month) experiment involving the burial and decay of small crustaceans. Our experimental design is innovative in that it models catastrophic sedimentation in fine‐grained colloidal suspension, which is believed to form Lagerstätten deposits. We demonstrated better preservation of buried organisms in clays compared to water, and in kaolinite compared to montmorillonite. As aluminium cations were present in high concentrations in kaolinite sediment but not in montmorillonite, the better preservation in kaolinite is attributed to the tanning properties of aluminium, which catalyses cross‐linking in proteins, protecting them from bacterial degradation. Anaerobic environments and acidification also slow down decay, but they are less effective than tanning. Kaolinite and montmorillonite replaced the crustacean integuments differently: in the remains buried in kaolinite, Al and Si were detected in equal proportions, while in those buried in montmorillonite, the Si content appeared to be much higher even in comparison with the initial sample of the clay. These variations probably arose from the different dynamics of acidic hydrolysis in the two clays associated with anaerobic decomposition of organic matter. Our results show that the preservation mechanism includes multi‐component interactions between the solution, mineral, sediment and organic remains; taken separately, any single component explains little. The specific conditions that occur within the colloidal clay sediments can facilitate conservation and start fast mineralization according to chemical properties and elemental content.     

Adsorption of reovirus to clay minerals: effects of cation-exchange capacity, cation saturation, and surface area.

The adsorption of reovirus to clay minerals has been reported by several investigators, but the mechanisms defining this association have been studied only minimally. The purpose of this investigation was to elucidate the mechanisms involved with this interaction. More reovirus type 3 was adsorbed, in both distilled and synthetic estuarine water, by low concentrations of montmorillonite than by comparable concentrations of kaolinite containing a mixed complement of cations on the exchange complex. Adsorption to the clays was essentially immediate and was correlated with the cation-exchange capacity of the clays, indicating that adsorption was primarily to negatively charged sites on the clays. Adsorption was greater with low concentrations of clays in estuarine water than in distilled water, as the higher ionic strength of the estuarine water reduced the electrokinetic potential of both clay and virus particles. The addition of cations (as chloride salts) to distilled water enhanced adsorption, with divalent cations being more effective than monovalent cations and 10(-2) M resulting in more adsorption than 10(-3) M. Potassium ions suppressed reovirus adsorption to montmorillonite, probably by collapsing the clay lattices and preventing the expression of the interlayer-derived cation-exchange capacity. More virus was adsorbed by montmorillonite made homoionic to various mono-, di-, and trivalent cations (except by montmorillonite homoionic to potassium) than by comparable concentrations of kaolinite homoionic to the same cations. The sequence of the amount of adsorption to homoionic montmorillonite was Al greater than Ca greater than Mg greater than Na greater than K; the sequence of adsorption to kaolinite was Na greater than Al greater than Ca greater than Mg greater than K. The constant partition-type adsorption isotherms obtained when the clay concentration was maintained constant and the virus concentration was varied indicated that a fixed proportion of the added virus population was adsorbed, regardless of the concentration of infectious particles. A heterogeneity within the reovirus population was indicated.     

Adsorption of reovirus to clay minerals: effects of cation-exchange capacity, cation saturation, and surface area

The adsorption of reovirus to clay minerals has been reported by several investigators, but the mechanisms defining this association have been studied only minimally. The purpose of this investigation was to elucidate the mechanisms involved with this interaction. More reovirus type 3 was adsorbed, in both distilled and synthetic estuarine water, by low concentrations of montmorillonite than by comparable concentrations of kaolinite containing a mixed complement of cations on the exchange complex. Adsorption to the clays was essentially immediate and was correlated with the cation-exchange capacity of the clays, indicating that adsorption was primarily to negatively charged sites on the clays. Adsorption was greater with low concentrations of clays in estuarine water than in distilled water, as the higher ionic strength of the estuarine water reduced the electrokinetic potential of both clay and virus particles. The addition of cations (as chloride salts) to distilled water enhanced adsorption, with divalent cations being more effective than monovalent cations and 10(-2) M resulting in more adsorption than 10(-3) M. Potassium ions suppressed reovirus adsorption to montmorillonite, probably by collapsing the clay lattices and preventing the expression of the interlayer-derived cation-exchange capacity. More virus was adsorbed by montmorillonite made homoionic to various mono-, di-, and trivalent cations (except by montmorillonite homoionic to potassium) than by comparable concentrations of kaolinite homoionic to the same cations. The sequence of the amount of adsorption to homoionic montmorillonite was Al greater than Ca greater than Mg greater than Na greater than K; the sequence of adsorption to kaolinite was Na greater than Al greater than Ca greater than Mg greater than K. The constant partition-type adsorption isotherms obtained when the clay concentration was maintained constant and the virus concentration was varied indicated that a fixed proportion of the added virus population was adsorbed, regardless of the concentration of infectious particles. A heterogeneity within the reovirus population was indicated.     

Effects of Water and pH on the Oxidative Oligomerization of Chloro an Methoxyphenol by a Montmorillonite Clay

This study focussed on the capacity of a montmorillonite clay to oxidize organic contaminants having activating (methoxyphenol) and deactivating (chlorophenol) substituent groups when pH and water conditions are changing. The amount and strength of Lewis and Br?nsted acidity of the clay was measured using organic indicator and titration methods. Water plays two distinct roles in the oxidation of such contaminants by clays: (1) it neutralizes the clay's Lewis acidity, thereby preventing chlorophenol from getting oxidized in significant yields; (2) it does not successfully compete with methoxyphenol for Lewis acid sites because high dimer yields are observed. The high capacity of Na⁺, Ca²⁺, and Fe³⁺ clays to oxidize phenolic compounds at high pH appears to be caused by phenolates being more reactive than the protonated form. The Lewis and Br?nsted acidity measurement of the various homoionic clays tested help explain the high capacity of the clays to oxidize phenolic compounds at low and high pH and their low capacity at near neutral pH. Finally, the results also clarify the effects of exchangeable cations on the capacity of clays to oxidize organic contaminants.     

Coloration changes of geologic media after addition of gasoline,diesel fuel,and ethylbenzene

The coloration changes of three soils (Amarillo sandy loam, Anthony sandy loam, and Oakville sandy loam) and two clays (kaolinite and montmorillonite) were monitored following the addition of four solvents (distilled water, unleaded gasoline, diesel fuel, and ethylbenzene) over a time period of 1 year. Soil and clay coloration was measured using Munsell color charts. In general, the Amarillo soil experienced the most extensive changes to a darker, grayer color. Initial color changes occurred in as little as 1 week, with subsequent changes occurring throughout the next 41 weeks. This study indicates that solvents can alter geologic media color and that the inferred chemical reduction processes can be an ongoing process.     

Protection of Nitrosomonas europaea colonizing clay minerals from inhibition by nitrapyrin

Nitrate production by Nitrosomonas europaea in inorganic liquid medium containing ammonium was limited by reduction in pH. In the presence of montmorillonite and vermiculite, expanding clays with high cation-exchange-capacity (CEC), nitrite yield was increased, ammonia oxidation continued at pH values below those which inhibited growth in the absence of clays and growth was biphasic. The first phase was similar to that in the absence of clays, while the second was characterized by a lower rate of nitrite production. Illite, a non-expanding clay with low CEC, had no significant effect on ammonia oxidation, while oxidation of ammonia-treated vermiculite (ATV) occurred with no significant change in the pH of the medium. ATV, montmorillonite and vermiculite, but not illite, protected cells from inhibition by nitrapyrin at concentrations inhibitory to cells growing in suspended culture. This protection was maintained in ATV homo-ionic to Al3+, but montmorillonite made homo-ionic to Al3+ did not provide protection from inhibition. Attachment of cells to clays with high CEC is therefore advantageous in providing exchange at the clay surface of NH+4 and H+ produced by ammonia oxidation, in reducing pH toxicity, and in protecting cells from inhibition.     

Role of the Interchangeable Cations on the Sorption of Fumaric and Succinic Acids on Montmorillonite and its Relevance in Prebiotic Chemistry

It has been proposed that clays could have served as key factors in promoting the increase in complexity of organic matter in primitive terrestrial and extraterrestrial environments. The aim of this work is to study the adsorption–desorption of two dicarboxylic acids, fumaric and succinic acids, onto clay minerals (sodium and iron montmorillonite). These two acids may have played a role in prebiotic chemistry, and in extant biochemistry, they constitute an important redox couple (e.g. in Krebs cycle) in extant biochemistry. Smectite clays might have played a key role in the origins of life. The effect of pH on sorption has been tested; the analysis was performed by UV–vis and FTIR-ATR spectroscopy, X-ray diffraction and X-ray fluorescence. The results show that chemisorption is the main responsible of the adsorption processes among the dicarboxylic acids and clays. The role of the ion, present in the clay, is fundamental in the adsorption processes of dicarboxylic acids. These ions (sodium and iron) were selected due to their relevance on the geochemical environments that possibly existed into the primitive Earth. Different mechanisms are proposed to explain the sorption of dicarboxylic acids in the clay. In this work, we propose the formation of complexes among metal cations in the clays and dicarboxylic acids. The organic complexes were probably formed in the prebiotic environments enabling chemical processes, prior to the appearance of life. Thus, the data presented here are relevant to the origin of life studies.

     

Optimization of an Iron Intercalated Montmorillonite Preparation for the Removal of Arsenic at Low Concentrations

A series of iron intercalated montmorillonites (Fe‐Monts) were prepared using (i) ion exchange of native sodium and calcium ions with iron ions, (ii) base hydrolysis of inserted iron ions in montmorillonite suspension, and (iii) insertion of pre‐hydrolyzed iron colloid in montmorillonite. The materials were characterized by X‐ray diffraction and gas adsorption‐desorption techniques. The basal d(001)‐spacing and BET specific surface area increased after the intercalation of iron species in montmorillonite. Local iron structure studied by X‐ray absorption fine structure (XAFS) spectroscopy showed an unsaturation of the Fe···Fe coordination number (N 2.5) of the intercalated iron species as compared to the bulk iron oxyhydroxides (N 6). The Fe‐Monts were employed for arsenic removal from aqueous solutions at low concentration (0.2–16 mg/L). Among the Fe‐Monts, the one prepared by the hydrolysis of inserted iron ions, was the best in performance. The saturation adsorption amount of the optimized iron‐montmorillonite was 4 and 28 times higher for the removal of arsenite and arsenate, respectively, as compared to bulk iron oxyhydroxide (goethite). Compared with bulk iron oxyhydroxide, the Fe‐Monts were superior for arsenate uptake and comparable for arsenite. In addition, arsenite adsorbed on the Fe‐Monts was found to be oxidized to arsenate based on XAFS spectroscopy.     

Adsorption of Adenine, Cytosine, Thymine, and Uracil on Sulfide-Modified Montmorillonite: FT-IR, M?ssbauer and EPR Spectroscopy and X-Ray Diffractometry Studies

In the present work the interactions of nucleic acid bases with and adsorption on clays were studied at two pHs (2.00, 7.00) using different techniques. As shown by Mössbauer and EPR spectroscopies and X-ray diffractometry, the most important finding of this work is that nucleic acid bases penetrate into the interlayer of the clays and oxidize Fe²⁺ to Fe³⁺, thus, this interaction cannot be regarded as a simple physical adsorption. For the two pHs the order of the adsorption of nucleic acid bases on the clays was: adenine????cytosine?>?thymine?>?uracil. The adsorption of adenine and cytosine on clays increased with decreasing of the pH. For unaltered montmorillonite this result could be explained by electrostatic forces between adenine/cytosine positively charged and clay negatively charged. However for montmorillonite modified with Na₂S, probably van der Waals forces also play an important role since both adenine/cytosine and clay were positively charged. FT-IR spectra showed that the interaction between nucleic acid bases and clays was through NH⁺ or NH ₂ ⁺ groups. X-ray diffractograms showed that nucleic acid bases adsorbed on clays were distributed into the interlayer surface, edge sites and external surface functional groups (aluminol, silanol) EPR spectra showed that the intensity of the line g????2 increased probably because the oxidation of Fe²⁺ to Fe³⁺ by nucleic acid bases and intensity of the line g?=?4.1 increased due to the interaction of Fe³⁺ with nucleic acid bases. Mössbauer spectra showed a large decreased on the Fe²⁺ doublet area of the clays due to the reaction of nucleic acid bases with Fe²⁺.     

New intercalated layer silicate nanocomposites based on synthesized starch-g-PCL prepared via solution intercalation and in situ polymerization methods: As a comparative study

Starch-g-polycaprolacton (Starch-g-PCL) nanocomposites have been prepared with graft polymerization through in situ ring-opening polymerization of ε-caprolacton in the presence of starch and Sn(Oct)₂ (Tin(II) 2-ethyl hexanoate) as an initiator/catalyst. A surface-modified montmorillonite by dimethyl (hydrogenated tallow alkyl) ammonium cation, was used. In fact, the related nanocomposites prepared via two methods in solution and in situ with introducing different amount of loading clay. The effect of swelling time on d-spacing of silicate layers was investigated and the obtained nanocomposites were analyzed using X-ray diffraction technique. The morphology of the synthesized nanocomposites examined using Scanning Electron Microscopy (SEM) and also the thermal degradation behavior of the prepared nanocomposites accomplished with using TGA.     

Effects of a clay mineral on microbial predation and parasitism ofEscherichia coli

Montmorillonitic clay influences the biological control ofEscherichia coli in aquatic systems, the magnitude of the effects being dependent on the state of the clay and the type of host-antagonist interaction. The interaction ofBdellovibrio andE. coli was partially inhibited by the presence of montmorillonite. Because it is highly motile,Bdellovibrio apparently could penetrate any colloidal clay barrier aroundE. coli if the clay envelope was thin enough. Colloidal clay had little effect on predation ofE. coli by the myxobacteriumPolyangium, and had no effect on the activity of the amoebaVexillifera. Crude clay, on the other hand, resulted in a physical separation of predator and prey, and this completely inhibited theE. coli-Polyangium interaction and slowed the rate of engulfment ofE. coli byVexillifera.The interference of natural biological control by clays may alter the microbial balance favoring survival of fecal microorganisms and resulting in their accumulation in saline sediments. This could constitute a health hazard if these organisms were released by upwelling of bottom waters or were desorbed in estuarine systems by dilution during heavy rains.     

Specificity of virus adsorption to clay minerals

Competitive adsorption studies indicated that reovirus type 3 and coliphage T1 did not share common adsorption sites on kaolinite and montmorillonite. Compounds in the minimal essential medium (e.g., fetal bovine serum, amino acids) in which the reovirus was maintained blocked adsorption of coliphage T1 to kaolinite and partially to montmorillonite in synthetic estuarine water, but they had no effect on coliphage adsorption to montmorillonite in distilled water or on the adsorption of the reovirus to either clay. The blockage of positively charged sites on kaolinite or montmorillonite by treatment of the clays with sodium metaphosphate or with the supernatants from montmorillonite or kaolinite, respectively, had no effect on adsorption of the reovirus. These data indicate that there was a specificity in adsorption sites for mixed populations of reovirus type 3 and coliphage T1 and emphasize the importance of using more than one type of virus, especially in combination, to predict virus behavior (e.g., adsorption, loss of infectivity) in soils and sediments containing clay minerals.     

The Fe-Rich Clay Microsystems in Basalt-Komatiite Lavas: Importance of Fe-Smectites for Pre-Biotic Molecule Catalysis During the Hadean Eon

During the Hadean to early Archean period (4.5–3.5 Ga), the surface of the Earth’s crust was predominantly composed of basalt and komatiite lavas. The conditions imposed by the chemical composition of these rocks favoured the crystallization of Fe-Mg clays rather than that of Al-rich ones (montmorillonite). Fe-Mg clays were formed inside chemical microsystems through sea weathering or hydrothermal alteration, and for the most part, through post-magmatic processes. Indeed, at the end of the cooling stage, Fe-Mg clays precipitated directly from the residual liquid which concentrated in the voids remaining in the crystal framework of the mafic-ultramafic lavas. Nontronite-celadonite and chlorite-saponite covered all the solid surfaces (crystals, glass) and are associated with tiny pyroxene and apatite crystals forming the so-called “mesostasis”. The mesostasis was scattered in the lava body as micro-settings tens of micrometres wide. Thus, every square metre of basalt or komatiite rocks was punctuated by myriads of clay-rich patches, each of them potentially behaving as a single chemical reactor which could concentrate the organics diluted in the ocean water. Considering the high catalytic potentiality of clays, and particularly those of the Fe-rich ones (electron exchangers), it is probable that large parts of the surface of the young Earth participated in the synthesis of prebiotic molecules during the Hadean to early Archean period through innumerable clay-rich micro-settings in the massive parts and the altered surfaces of komatiite and basaltic lavas. This leads us to suggest that Fe,Mg-clays should be preferred to Al-rich ones (montmorillonite) to conduct experiments for the synthesis and the polymerisation of prebiotic molecules.     

Chemical evolution 40. clay-mediated oxidation of diaminomaleonitrile

Summary The previously reported inhibition of the oligomerization of HCN by montmorillonite clays was investigated. The inhibition is due to the oxidation of diaminomaleonitrile (DAMN) by the Fe³⁺ in the clay lattice. Fe²⁺ and oxalic acid were shown to be the reaction products. From these reaction products and the previous report that two equivalents of HCN are formed per equivalent ofDAMN, it was established that diiminosuccinonitrile (DISN) is the initial reaction product, which is rapidly hydrolyzed to oxalic acid and HCN. The same oxidative transformations are effected by Fe³⁺ bound to Dowex 50, Fe³⁺ in solution and Ni(NH₃)₆ ²⁺. The rate of reaction of DAMN decreased in the order Fe³⁺ > Fe³⁺-Dowex > montmorillonite, indicating no catalytic role for the clay in the oxidation of DAMN. Little reaction of DAMN was observed with montmorillonite in which the bulk of the iron was in the Fe²⁺ oxidation state. The possible significance of these redox reactions to chemical evolution is discussed.For the previous papers in this series see Ferris JP, Alwis KW, Edelson EH, Mount N, Hagan Jr J (1980) Origin of Life Wolman Y (ed) Reidel, Dordrecht, p 125–128 Ferris JP, Edelson EH, Auyeung JM, Joshi PC (1981) J Mol Evol 17:69-77     

Controlling harmful algal blooms through clay flocculation

The potential use of clays to control harmful algal blooms (HABs) has been explored in East Asia, Australia, the United States, and Sweden. In Japan and South Korea, minerals such as montmorillonite, kaolinite, and yellow loess, have already been used in the field effectively, to protect fish mariculture from Cochlodinium spp. and other blooms. Cell removal occurs through the flocculation of algal and mineral particles, leading to the formation of larger aggregates (i.e. marine snow), which rapidly settle and further entrain cells during their descent. In the U.S., several clays and clay-rich sediments have shown high removal abilities (e.g. > 80% cell removal efficiency) against Karenia brevis, Heterosigma akashiwo, Pfiesteria piscicida and Aureococcus anophagefferens. In some cases, the removal ability of certain clays was further enhanced with chemical flocculants, such as polyaluminum chloride (PAC), to increase their adhesiveness. However, cell removal was also affected by bloom concentration, salinity, and mixing. Cell mortality was observed after clay addition, and increased with increasing clay concentration, and prolonged exposure to clays in the settled layer. Mesocosm, field enclosure, and flume experiments were also conducted to address cell removal with increasing scale and flow, water-column impacts, and the possible benthic effects from clay addition. Results from these studies will be presented, especially those in regards to water quality, seawater chemistry, bottom erodibility and faunal impacts in the benthos. At this time, clay dispersal continues to be a promising method for controlling HABs and mitigating their impacts based on existing information and experimental data.