Organic-mineral Interface Research Articles

Environmental implications of interaction between humic substances and iron oxide nanoparticles: A review.

Goethite, hematite, ferrihydrite, and other iron oxides bind through various sorption reactions with humic substances (HS) in soils creating nano-, micro-, and macro-aggregates with a specific nature and stability. Long residence times of soil organic matter (SOM) have been attributed to iron-humic substance (Fe-HS) complexes due to physical protection and chemical stabilization at the organic-mineral interface. Humic acids (HA) and fulvic acids (FA) contain many acidic functional groups that interact with Fe oxides through different mechanisms. Due to the numerous interactions between mineral Fe and natural SOM, much research has led into a better identification and definition of HS. In this review, we first focus on the surface colloidal properties of Fe oxides and their reactivity toward HS. These minerals can be efficiently identified by usual techniques, such as XRD, FTIR spectroscopy, XAS, Mössbauer, diffuse reflectance spectroscopies (DRS), HRTEM, ATM, NanoSIMS. Second, we present the recent state of art regarding the adsorption/precipitation of HS onto iron mineral surfaces and their effects on binding metalloid and trace elements. Finally, we consider future research directions based on recent scientific literature, with particular focus on the ability of Fe nano-particles to increase Fe bioavailability, improve carbon sequestration, reduce greenhouse gas emissions, and decrease the impact of persistent organic and inorganic pollutants. The methodology in this field has rapidly developed over the last decade. However, new procedures to estimate the nature of Fe-HA bonds will be important contributions in clarifying the role of natural iron oxides in soil for carbon stabilization.

Supercritical methane adsorption and storage in pores in shales and isolated kerogens

Shale gas is an important hydrocarbon resource in a global context. It has had a significant impact on energy resources in the US, but the worldwide development of this methane resource requires further research to increase the understanding of the relationship of shale structural characteristics to methane storage capacity. In this study a range of gas adsorption, microscopic, mercury injection capillary pressure porosimetry and pycnometry techniques were used to characterize the full range of porosity in a series of shales of different thermal maturity. Supercritical methane adsorption methods for shale under conditions which simulate geological conditions (up to 473 K and 15 MPa) were developed. These methods were used to measure the methane adsorption isotherms of Posidonia shales where the kerogen maturity ranged from immature, through oil window, to gas window. Subcritical methane and carbon dioxide adsorption studies were used for determining pore structure characteristics of the shales. Mercury injection capillary pressure porosimetry was used to characterize the meso and macro porosity of shales. The sum of the CO2 sorption pore volume at 195 K and mercury injection capillary pressure pore volumes (1093–5.6 nm) were equal to the corresponding total pore volume (< 1093 nm) thereby giving an equation accounting for virtually all the available shale porosity. These measurements allowed quantification of all the available porosity in shales and were used for estimating the contributions of methane stored as ‘free’ compressed gas and as adsorbed gas to overall methane storage capacity of shales. Both the mineral and kerogen components of shale were studied by comparing shale and the corresponding isolated kerogens so that the relative contributions of these components could be assessed. The results show that the methane adsorption characteristics were much higher for the kerogens and represented 35–60% of the total adsorption capacity for the shales used in this study, which had total organic contents in range 5.8–10.9 wt%. Microscopy studies revealed that the pore systems in clay-rich, organic-rich and microfossil-rich parts of shale are very different, and also the importance of the inter-granular organic-mineral interface.

XPS and two-dimensional FTIR correlation analysis on the binding characteristics of humic acid onto kaolinite surface

The stabilization and preservation of soil organic matter have been attributed to the strong reactive sites of mineral surfaces that cause physical isolation and chemical stabilization due to the organic-mineral interface. However, much of the micro-scale knowledge about interactions between organic ligands and minerals largely remains at the qualitative level, and neglects the heterogeneity of functional groups of organic matter. Here, we report the use of molecular-scale technologies of two-dimensional FTIR Correlation Spectroscopy (2D-FTIR-CoS) and X-ray Photoelectron Spectroscopy (XPS) to directly measure the binding processes of humic acid (JGHA) groups onto kaolinite surface. The spectroscopy results showed that the carboxylate groups, aliphatic OH and aromatic structure participate in the binding of JGHA on kaolinite surface. The carboxylic and phenolic hydroxyl interact with kaolinite surface through the interfacial COAl/Si bonds. Kaolinite prefers to adsorb C-groups at pH 4.0 and O-groups at pH 8.0. The interaction of COO– group at 1566 cm−1 of JGHA leads to the formation of inner-sphere complex first and then outer-sphere complex with increasing contact time. The interaction of COOH group at 1261 cm−1 with the AlOH2+ of kaolinite was could be ascribed to ligand exchange and/or electrostatic attraction, whose contribution was evaluated to be 13.90%, 7.65% and 0% at pH 4.0, 6.0 and 8.0, respectively. These results of molecular binding provide quantitative mechanistic insights into organic-mineral interactions and expound the effect of functional groups of HA on binding mechanisms, and thus bring important clues for better understanding the mobility and transformation of land‑carbon including mineral-bound carbon.

Heat transfer within frozen slopes in subarctic Yukon, Canada

The dominant mechanism of heat transfer during ground thaw is typically assumed to be vertical conduction. However, the addition of lateral subsurface water flow introduces the potential for the forced convection of energy, having an influence on ground temperatures and thaw rates. Field observations of snowmelt run-off and rates of ground thaw for two slopes within the Wolf Creek basin, Yukon, Canada, highlighted different rates of ground thaw with slope position. Ground temperatures were numerically simulated to evaluate the relative influence of conduction and convection on the thawing of these slopes; each slope comprised different soils and had a different slope aspect. Both slopes were composed of an organic layer overlying a mineral soil. Lateral water flow above the frozen layer occurred within both slopes as a result of a perched saturated zone above the organic–mineral interface. The numerical models reveal that lateral diversion within a surficial, high-hydraulic conductivity layer, such as an organic layer, can initiate convective heat transfer. However, the observed differential thaw was determined to be a result of conduction and variations in the initial ice content and snow cover rather than lateral convection of heat.

Hierarchical integration of porosity in shales

Pore characterization in shales is challenging owing to the wide range of pore sizes and types present. Haynesville-Bossier shale (USA) was sampled as a typical clay-bearing siliceous, organic-rich, gas-mature shale and characterized over pore diameters ranging 2 nm to 3000 nm. Three advanced imaging techniques were utilized correlatively, including the application of Xe+ plasma focused ion beam scanning electron microscopy (plasma FIB or PFIB), complemented by the Ga+ FIB method which is now frequently used to characterise porosity and organic/inorganic phases, together with transmission electron microscope tomography of the nano-scale pores (voxel size 0.6 nm; resolution 1–2 nm). The three pore-size scales each contribute differently to the pore network. Those <10 nm (greatest number), 10 nm to 100 nm (best-connected hence controls transport properties), and >100 nm (greatest total volume hence determines fluid storativity). Four distinct pore types were found: intra-organic, organic-mineral interface, inter-mineral and intra-mineral pores were recognized, with characteristic geometries. The whole pore network comprises a globally-connected system between phyllosilicate mineral grains (diameter: 6–50 nm), and locally-clustered connected pores within porous organic matter (diameter: 200–800 nm). Integrated predictions of pore geometry, connectivity, and roles in controlling petrophysical properties were verified through experimental permeability measurements.

Charcoal in Organic Horizon and Surface Mineral Soil in a Boreal Forest Fire Chronosequence of Western Quebec: Stocks, Depth Distribution, Chemical Properties and a Synthesis of Related Studies

Wildfires are a major driver of carbon stocks and ecosystem development in Canadian boreal forests, but there is little information on amounts and properties of the charcoal produced. Using data and samples available from a previous study, we determined amounts, depth distribution and chemical properties of visually-determined charcoal (> 2 mm) in a boreal chronosequence in the Abitibi region of Quebec, Canada. Sites ranged from 24 to 2355 years since fire (ysf) and originated from low- and high-severity soil burns (> 5 cm or < 5 cm organic horizon unburned, respectively). Two or three pits were sampled at 1-cm depth intervals from 20 jack pine (Pinus banksiana) sites (one low severity and 19 high severity) and 31 black spruce (Picea mariana) sites (12 low severity and 19 high severity). Site-level charcoal stocks ranged from 50 to 5527 kg ha-1 with high within-site variability and lower stocks for the oldest sites. Depth distributions typically peaked around the organic-mineral interface, but some low-severity sites also had charcoal layers within the organic horizon. Means from 30 samples were 569 mg g-1 total C, 4.1 mg g-1 total N and 140 C/N (molar), with total C and C/N showing a trend of decline with time since fire, and total N showing an increase. Solid-state 13C CPMAS NMR spectra of nine samples showed high variability among the younger samples, but a trend to higher aromaticity for the older ones. A literature survey focusing on boreal forests similarly showed highly variable stocks and chemical properties of charcoal in organic horizon and upper mineral soil, with reduction of variance and lower stocks after several hundred years. This initial variation was also consistent with reports of highly variable temperatures and duration of charring in wildfires. Adding reports available for char production, and considering that most studies of char stocks and production are limited to the organic horizon (forest floor), suggests that initial production of charred material from boreal wildfires might be around 5-10 tonnes ha-1.

Developing a molecular picture of soil organic matter\u2013mineral interactions by quantifying organo\u2013mineral binding

Long residence times of soil organic matter have been attributed to reactive mineral surface sites that sorb organic species and cause inaccessibility due to physical isolation and chemical stabilization at the organic–mineral interface. Instrumentation for probing this interface is limited. As a result, much of the micron- and molecular-scale knowledge about organic–mineral interactions remains largely qualitative. Here we report the use of force spectroscopy to directly measure the binding between organic ligands with known chemical functionalities and soil minerals in aqueous environments. By systematically studying the role of organic functional group chemistry with model minerals, we demonstrate that chemistry of both the organic ligand and mineral contribute to values of binding free energy and that changes in pH and ionic strength produce significant differences in binding energies. These direct measurements of molecular binding provide mechanistic insights into organo–mineral interactions, which could potentially inform land-carbon models that explicitly include mineral-bound C pools.

X-ray micro-beam techniques and phase contrast tomography applied to biomaterials

A deeper comprehension of the biomineralization (BM) process is at the basis of tissue engineering and regenerative medicine developments. Several in-vivo and in-vitro studies were dedicated to this purpose via the application of 2D and 3D diagnostic techniques. Here, we develop a new methodology, based on different complementary experimental techniques (X-ray phase contrast tomography, micro-X-ray diffraction and micro-X-ray fluorescence scanning technique) coupled to new analytical tools. A qualitative and quantitative structural investigation, from the atomic to the micrometric length scale, is obtained for engineered bone tissues. The high spatial resolution achieved by X-ray scanning techniques allows us to monitor the bone formation at the first-formed mineral deposit at the organic–mineral interface within a porous scaffold. This work aims at providing a full comprehension of the morphology and functionality of the biomineralization process, which is of key importance for developing new drugs for preventing and healing bone diseases and for the development of bio-inspired materials.

NMR investigation of the role of osteocalcin and osteopontin at the organic-inorganic interface in bone.

Mechanical resilience of bone tissue decreases with age. The ability to comprehensively probe and understand bone properties could help alleviate this problem. One important aspect of bone quality that has recently been made evident is the presence of dilatational bands formed by osteocalcin (OC) and osteopontin (OPN), which contribute to fracture toughness. However, experimental evidence of the structural role of these two proteins at the organic-mineral interface in bone is still needed. Solid state nuclear magnetic resonance (SSNMR) is emerging as a useful technique in probing molecular level aspects of bone. Here, we present the first SSNMR study of bone tissue from genetically modified mice lacking OC and/or OPN. Probing the mineral phase, the organic matrix and their interface revealed that, despite the absence of OC and OPN, the organic matrix and mineral were well preserved, and the overall exposure of collagen to hydroxyapatite (HA) nanoparticles was hardly affected. However, the proximity to the HA surface was slightly increased for a number of bone components including less abundant amino acids like lysine, suggesting that this is how the tissue compensates for the lack of OC and OPN. Taken together, the NMR data supports the recently proposed model, in which the contribution of OC-OPN to fracture toughness is related to their presence at the extrafibrillar organic-mineral interfaces, where they reinforce the network of mineralized fibrils and form dilatational bands. In an effort toward further understanding the structural role of individual amino acids of low abundance in bone, we then explored the possibility of specific (13)C enrichment of mouse bone, and report the first SSNMR spectra of 97% (13)C lysine-enriched tissue. Results show that such isotopic enrichment allows valuable molecular-level structural information to be extracted, and sheds light on post-translational modifications undergone by specific amino acids in vivo.

Early stage mineralization in tissue engineering mapped by high resolution X-ray microdiffraction

The specific routes of biomineralization in nature are here explored using a tissue engineering approach in which bone is formed in porous ceramic constructs seeded with bone marrow stromal cells and implanted in vivo. Unlike previous studies this model system reproduces mammalian bone formation, here investigated at high temporal resolution. Different mineralization stages were monitored at different distances from the scaffold interface so that their spatial analysis corresponded to temporal monitoring of the bone growth and mineralization processes. The micrometer spatial resolution achieved by our diffraction technique ensured highly accurate reconstruction of the different temporal mineralization steps and provided some hints to the challenging issue of the mineral deposit first formed at the organic–mineral interface. Our results indicated that in the first stage of biomineralization organic tissue provides bioavailable calcium and phosphate ions, ensuring a constant reservoir of amorphous calcium phosphate (ACP) during hydroxyapatite (HA) nanocrystal formation. In this regard we suggest a new role of ACP in HA formation, with a continuous organic–mineral transition assisted by a dynamic pool of ACP. After HA nanocrystals formed, the scaffold and collagen act as templates for nanocrystal arrangement on the microscopic and nanometric scales, respectively.

Solid state NMR investigation of intact human bone quality: balancing issues and insight into the structure at the organic-mineral interface.

Age-related bone fragility fractures present a significant problem for public health. Measures of bone quality are increasingly recognized to complement the conventional bone mineral density (BMD) based assessment of fracture risk. The ability to probe and understand bone quality at the molecular level is desirable in order to unravel how the structure of organic matrix and its association with mineral contribute to the overall mechanical properties. The (13)C{(31)P} REDOR MAS NMR (Rotational Echo Double Resonance Magic Angle Spinning Nuclear Magnetic Resonance) technique is uniquely suited for the study of the structure of the organic-mineral interface in bone. For the first time, we have applied it successfully to analyze the structure of intact (non-powdered) human cortical bone samples, from young healthy and old osteoporotic donors. Loading problems associated with the rapid rotation of intact bone were solved using a Finite Element Analysis (FEA) approach, and a method allowing osteoporotic samples to be balanced and spun reproducibly is described. REDOR NMR parameters were set to allow insight into the arrangement of the amino acids at the mineral interface to be accessed, and SVD (Singular Value Decomposition) was applied to enhance the signal to noise ratio and enable a better analysis of the data. From the REDOR data, it was found that carbon atoms belonging to citrate/glucosaminoglycans (GAGs) are closest to the mineral surface regardless of age or site. In contrast, the arrangement of the collagen backbone at the interface varied with site and age. The relative proximity of two of the main amino acids in bone matrix proteins, hydroxyproline and alanine, with respect to the mineral phase was analyzed in more detail, and discussed in view of glycation measurements which were carried out on the tissues. Overall, this work shows that the (13)C{(31)P} REDOR NMR approach could be used as a complementary technique to assess a novel aspect of bone quality, the organic-mineral interface structure.

Probing the Organic−Mineral Interface at the Molecular Level in Model Biominerals

It is widely known that macromolecules, such as proteins, can control the nucleation and growth of inorganic solids in biomineralizing organisms. However, what is not known are the complementary molecular interactions, organization, and rearrangements that occur when proteins interact with inorganic solids during the formation of biominerals. The organic-mineral interface (OMI) is expected to be the site for these phenomena, and is therefore extraordinarily interesting to investigate. In this report, we employ X-ray absorption near edge (XANES) spectromicroscopy to investigate the electronic structure of both calcium carbonate mineral crystals and polypeptides, and detect changing bonds at the OMI during crystal growth in the presence of polypeptides. We acquired XANES spectra from calcium carbonate crystals grown in the presence of three mollusk nacre-associated polypeptides (AP7N, AP24N, n16N) and in the presence of a sea urchin spicule matrix protein, LSM34. All these model biominerals gave similar results, including the disruption of CO bonds in calcite and enhancement of the peaks associated with C-H bonds and C-O bonds in peptides, indicating ordering of the amino acid side chains in the mineral-associated polypeptides and carboxylate binding. This is the first evidence of the mutual effect of calcite on peptide chain and peptide chain on calcite during biomineralization. We also show that these changes do not occur when Asp and Glu are replaced in the n16N sequence with Asn and Gln, respectively, demonstrating that carboxyl groups in Asp and Glu do participate in polypeptide-mineral molecular associations.

A comparative EPR, infrared and Raman study of natural and deproteinated tooth enamel and dentin

The aim of the present work was to investigate how the native signal observed in the electron paramagnetic resonance (EPR) spectrum of tooth enamel and dentin is associated with the organic content of the two tissues. This was achieved by comparing the EPR native signal and the optical bands (Raman and infrared, IR) associated with organic components of tooth enamel and dentin, in natural and deproteinated samples. The main results were: (a) in natural samples, the organic optical bands are more intense in dentin than in enamel, in contrast with the EPR native signal which shows similar intensity in the two tissues; (b) after deproteination, the optical organic bands are completely suppressed in both dentin and enamel, while the EPR native signal is eliminated only in dentin. It is suggested that the IR and Raman organic bands are originated in the bulk of the organic matrix, while the paramagnetic centres associated with the EPR native signal are located in the organic–mineral interface.

The Organic-Mineral Interface in Biominerals

Numerous living organisms form minerals. These biogenic minerals, or biominerals, are composite materials containing an organic matrix and nano- or micro-scale amorphous or crystalline minerals. In this chapter we will review the molecular aspects of biomineralization and describe as completely as is currently possible the organic-mineral interface, the location in which organic-mineral interactions occur. Biomineral composite materials include bone, dentine, enamel, statoliths, otoliths, mollusk and crustacean shells, coccolith scales, eggshells, sponge silica skeletons, algal, radiolarian and diatom silica micro-shells, and a variety of transition metal minerals produced by different bacteria (Lowenstam and Weiner 1989; Addadi and Weiner 1997; Banfi eld and Nealson 1997; Fortin et al. 1997; Fitts et al. 1999; Templeton et al. 1999; Lower et al. 2001a; Mann 2001; Glasauer et al. 2002; De Yoreo and Vekilov 2003; Weiner and Dove 2003; De Yoreo and Dove 2004).From a materials science perspective, organic molecules are soft, compliant and fracture resistant while inorganic crystals are hard and brittle. Biomineral composites combine the best of these properties and minimize the weaknesses: they are both hard and fracture resistant (tough) (Currey 1977; Jackson et al. 1988; Schaffer et al. 1997; Kamat et al. 2000; Gao et al 2003). This is due to several factors: structure, nano-size and chemical composition. Only recently materials scientists have begun to learn how to build a synthetic composite material that outperforms each component taken separately, and have done so inspired by shell nacre (Tang et al. 2003).The mechanisms of biomineral formation are not fully understood (Mount et al. 2004) and while they are of interest in their own right, they may also provide models for new materials concepts, inspire design solutions and give new insights into the genetic control of biological structure (e.g., Schaffer et al. 1997).Lowenstam (1981) introduced the distinction between the biologically induced mineralization, which is enacted extracellularly or on the cell surface by many algae and bacterial species, and the organic-matrix mediated mineralization performed by many animals (later termed biologically controlled mineralization) (Bazylinski and Frankel 2003; Frankel and Bazylinski 2003; Veis 2003).Eukaryotic biominerals often show complex hierarchical structure from the nanometer to the macroscopic scale. This structure confers mechanical strength and toughness: despite being highly mineralized, with the organic component constituting not more than a few percent of the composite material, the fracture toughness exceeds that of single crystals of the

Transport of conservative and reactive tracers through a naturally structured upland podzol field lysimeter

Compared to agricultural soils, descriptions of solute transport in upland soils at scales smaller than catchments are scarce. This study evaluates data from three consecutive field tracer experiments in which Cl, Na and Ca (stepped rates of 4.5, 9 and 4.5 mm h −1) were irrigated onto a ferric podzol monolith (3×2 m 2 and 0.6 m depth) isolated from the surrounding soil except at the base. For each individual experiment a one hour pulse of tracer was applied and subsequently washed through with water for approximately 1 pore volume and monitored using suction cup samplers located in the O and B horizons. Breakthrough curves showed considerable heterogeneity in the response of both horizons and inferred that downward leaching would result in considerable temporal spreading of solute mass across wide time scales. Patterns of Cl and Na breakthrough were similar and were characterised by low peak concentrations (maximum C/C 0 of 0.05 Cl and 0.03 Na). Minimal Ca breakthrough was observed in the O horizon, although a higher breakthrough was observed in the B horizon. These factors suggest that isolated highly active pathways were controlling the O horizon response, although these were not captured by the sampler network. This was supported by more rapid mean times to peak in the B horizon. Lateral drainage, intercepted at the base of the O horizon on the downslope face, accounted for approximately 45% of solute volume and 25, 21 and 14% of Cl, Na and Ca tracer mass, respectively. This rapid drainage pathway comprised surface flow and flow along the organic mineral interface, likely fed from preferential flow pathways in the O horizon. The breakthroughs observed in the mineral soil, although heterogeneous, indicated a response for this horizon of sustained leaching to shallow ground waters.

Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analyses of mineral and organic matrix during heating of mother of pearl (nacre) from the shell of the mollusc Pinctada maxima.

Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction patterns were used to analyze the mineral structure and organic matrix composition and thermal behavior of the internal nacreous layer (mother of pearl or nacre) of the shell of the giant oyster Pinctada maxima. Nacre is a natural biomaterial with osteogenic properties. The mineral of nacre is calcium carbonate crystallized as aragonite and it is highly crystallized. The FT-IR spectra showed amide, amine, and carboxylic acid groups in the organic matrix of the whole (organic and mineral) nacreous layer, with the HCO(-)(3) groups possibly at the organic-mineral interface. The insoluble organic matrix remaining after decalcification contained amide, amine, and carboxylic groups. The heated aragonite mineral structure of nacre underwent two transformations (X-ray diffraction), aragonite to calcite at 300-400 degrees C, and calcite to calcium oxide (CaO) at 500-600 degrees C. The organic matrix of nacre was destroyed around 550-600 degrees C, the same temperature as the calcite to CaO transformation, revealing the great thermal stability of the organic matrix and the organic-mineral bonding. This could be an useful feature for the in vivo use of this natural biomaterial as an implant.

In-situ Study of Organic Monolayer Adsorption on Calcite Using X-ray Scattering Techniques

The presence of dissolved organic compounds is known to have a profound impact upon the dissolution and growth of minerals[I], and the controlled nucleation of minerals at organic membrane surfaces is suspected to be an important feature of the formation of the exoskeletons of many invertebrate species[2]. Consequently, a fundamental understanding of the organic-mineral interface is of wide interest to many fields. Yet there are relatively few experimental tools which are capable of following the in situ formation and growth of organic films at the mineral-fluid interface. Here we describe some recent results obtained using X-ray scattering techniques to measure a well-defined model system: the adsorption of stearic acid monolayers at a calcite surface.

Cellulose decomposition in southeast Alaskan forests: effects of pit and mound microrelief and burial depth

In southeast Alaska, where wildfires are rare, uprooting is the predominant disturbance influencing stand development in Tsugaheterophylla (Raf.) Sarg. – Piceasitchensis (Bong.) Carr. forests. We compared 1-year decomposition of confined cellulose filter paper placed in the organic horizon and at the organic–mineral interface on both tree-throw mounds and adjacent pits. Decomposition rates were not significantly different between pits and mounds, but filter papers within the organic layer lost 33.7% of their original dry mass, and packs within the mineral layer lost 14.5% of their mass. This effect was highly significant (p &lt; 0.01). We concluded that the greater organic accumulations observed in pits are largely due to litter redistribution.

Snowmelt runoff modeling in a balsam fir forest with a variable source area simulator (VSAS2)

The variable source area model of storm flow generation VSAS2 has been adapted to simulate snowmelt runoff in the Lac Laflamme forested basin, 80 km north of Quebec City. The model has been adapted to accept different water inputs according to topography, to factor the effect of lake water storage in the discharge hydrograph and to process 3 months of hourly data. To ensure convergence of the mathematical solution, the explicit form of flow equations included in VSAS2 has been transformed to use an iterative approach. Lysimeter measurements as well as outputs from the snowmelt temperature index model SNOW‐17 were used as input data in the simulation. Results showed that low flows in early spring were well reproduced by the physically based model. However, all seasonal (1985, 1986 and 1987) peak flows were underestimated when all water input was considered to infiltrate. Observations on the site showed that the natural topographical drainage network was augmented in the spring by superficial concrete frost, pipe throughflow at the organic‐mineral soil interface and snowpack basal ice layers. It was therefore necessary to use an infiltrability index to improve the model. Because it was closely related to the development of an impervious layer at the soil surface, the relative proportion of bare ground areas on the basin was also related to the rising of streamflow hydrographs. Thus values of snow cover areal extent were taken from SNOW‐17 outputs and used as an index to the prevailing conditions of soil infiltrability on the basin. Results from VS AS2 were greatly improved, supporting the hypothesis of an important surface flow contribution during late snowmelt. The study underlined the necessity of further field investigations on the dynamics of infiltration processes into frozen soil.

TWO ELECTRIC POTENTIAL SIGNATURES OF SERIAL DIURNAL FROST

During a 96-hour period in mid-March 1987, a series of four serial frost-thaw events occurred in a research field at the University of Michigan Matthaei Botanical Gardens. Soil temperature and electric potential were recorded at two near surface probe arrays (0, 3, 6 & 9 cm) and (0, 5, 10 & 15 cm) with a horizontal separation of approximately 1 m beneath the organic-mineral soil interface at hourly intervals. These time series revealed strong repetitive serial patterns. When the electric potential measurements were converted to a surrogate measure of electrolyte concentration, the C-index, strong coupled flow effects appeared to be present in the time series owing to the effects of surface freeze-thaw, evaporation-distillation and soil water advection. The data set shows the low frequency effects of upward soil water advection increasing the soil temperature and modulating the electrolyte concentration. These observations also demonstrate that soil freezing processes have two distinct regimes dominated by...