Characterization of the Nonesuch Formation, middle unit of the Proterozoic Oronto Group, as a potential hydrocarbon source for the Lake Superior basin portion of the Midcontinent Rift system requires an understanding of the thermal maturity of the region and its relationship to the thermal history. Illite/smectite (I/S) expandability data were collected from the Nonesuch Formation and the overlying Freda Sandstone and compared with organic thermal maturity data; both data sets coupled with a thermal and burial history for the White Pine area of Michigan allow regional interpretation of maximum formation temperatures of the Nonesuch Formation and the Freda Sandstone with respect to time. Samples collected from drill holes in northeastern Wisconsin display nearly pure smectite within the lower Freda Sandstone trending abruptly to ordered I/S within the Nonesuch Formation. Regular trends of decreasing expandability with depth occur in four other drill holes to the northeast. Comparison of I/S expandability between similar stratigraphic intervals reveals a significant trend of increasing thermal maturity to the northeast, with the lowest thermal maturities observed in the Iron River Syncline area just west of White Pine, Michigan.

I/S geothermometry suggests maximum temperatures in the Nonesuch Formation of 140°C in Wisconsin, 115°C in the Iron River Syncline area, 160°C at White Pine, and 190°C near the southern portions of the Keweenaw Copper District. The geographic pattern of temperatures determined from I/S geothermometry is identical to that determined from organic thermal maturity indicators in the Nonesuch Formation (Imbus et al., 1988, 1990; Hieshima and Pratt, 1991; Pratt et al, 1991; Mauk and Hieshima, 1992).

Regular variations in I/S expandability with depth occur in the Freda Sandstone and the Nonesuch Formation near the southern limits of the Keweenaw Copper District. These variations suggest a fossil geothermal gradient of 55°C/km and limit the thickness of sediment above the Nonesuch Formation to approximately 3 km. In comparison, 3.6 km of Freda Sandstone are presently exposed near the Wisconsin border, and numerical modeling suggests a range of 4–6 km of sediment overlying the Nonesuch Formation. None of the data indicate the presence of the Bayfield Group sediments above the Nonesuch Formation at the time of clay diagenesis. Samples from White Pine suggest a two-stage burial history: 1) clay reaction, possible hydrocarbon maturation, and copper-sulfide mineralization at maximum temperatures above 100°C during the main rifting and burial event, followed by 2) fracturing, reverse faulting, and fluid circulation during a rift-terminating compressional event that may have allowed petroleum migration and native copper mineralization at temperatures below 100°C. Abrupt changes in I/S expandability with depth and the presence of poorly crystalline I/S (greater than 80% expandable) and kaolinite in the Freda Sandstone in Wisconsin appear to represent later overprinting of the diagenetic assemblage by fluids that were probably cooler and of differing composition than earlier diagenetic fluids. However, the authigenic assemblage from the vicinity of White Pine, Michigan, which includes up to 25% expandable I/S, appears to represent a diagenetic profile formed during the main rifting and burial event. Therefore, these expandable I/S-type clays are essentially 1.0 billion years old.

Mineralizable macronutrients (e.g. C, N, P, and S) are sorbed readily (i.e. adsorption and precipitation) in clays and clay minerals. Phosphorus (P) is one of the limiting macronutrients in soils because both phosphate and organic P undergo chemisorption in soil minerals. Furthermore, phosphatases that mineralize the organic P species tend to partition into soil minerals, suppressing the interactions between organic P and phosphatase. Adsorbed phosphatase on the mineral surfaces can regulate the enzyme activity and influence the biochemical properties of the enzyme (e.g. kinetics, conformation, and stability), affecting the P cycle in the terrestrial environment. Phosphatase–mineral interactions are widely reported to decrease the enzyme activity while enhancing the enzyme stability (e.g. thermal and proteolysis stability). Contradictory findings have also been reported. Specific enzymes, mineral characteristics, and reaction conditions are probably responsible for various reactivity (e.g. mineralization). The purpose of the present review was to summarize current and past investigations of acid and alkaline phosphatase sorption in clays and clay minerals and to examine phosphatase chemical properties (e.g. kinetic activity, thermal and proteolysis stability) and factors (e.g. pH, saturating cations of the mineral, enzyme structure, and mineral surface polarity) influencing the phosphatase-mineral interaction. Lastly, also reviewed is the application of phosphatase–mineral interactions with some expansion to other enzymes as an indication of potential future application for phosphatase and future research needs.

Many studies have improved our understanding of the mode of preservation at the Crato fossil Lagerstätte. The high degree of preservation of the Crato mineralized insects is thought to be a consequence of the diffusion of ions through carcasses and envelopment by bacteria that, in turn, created microenvironmental conditions that led to mineralization, mainly pyritization. Pyritized insects have been oxidized by in situ weathering to more stable oxide/hydroxy minerals during Quaternary time. This transformation is essential to maintain the palaeontological information acquired during microbially induced pyritization in an oxidizing atmosphere. However, intense weathering can diminish or obscure the morphological fidelity, and little attention has been paid to the post-diagenetic processes experienced by these fossils. Here, we aim to determine the degree of alteration undergone by Crato pyritized insects using the following combination of analytical tools: scanning electron microscopy, energy dispersive X-ray spectroscopy, Fourier transform infrared and Raman spectroscopy. Our results show that well-preserved insects are preferentially replaced by haematite and poorly preserved fossils are replaced by goethite. In addition, we recorded three types of post-diagenetic alteration: insects with iron-oxide overgrowths; insects associated with black coatings, sometimes with the formation of dendrites; and insects preserved as an impression, where only the outline of the body remains. All of these alterations have the potential to distort or tarnish palaeontological information. Here, we measured the effects of such telodiagenetic alterations at macro and micro scales. Therefore, this taphonomic approach has wide applicability wherever fine-grained deposits bearing mineralized insects are found.

On soils dominated by high proportions of clay and organic matter, soil acidity and poor nutrient use efficiency have a major impact on output potential. Due to the inherent chemical properties of these soils, reducing soil acidity and the prevalence of undesirable metallic cations poses challenges. As a result, these soils have a large capacity for phosphorus (P) fixation, therefore reducing plant P availability. Limestone (CaCO3 or MgCO3) is applied to agricultural soils to counteract soil acidity and reduce P fixation. The current study investigates the effects of four contrasting annual P application rates (0, 50, 100, 150 kg P/ha); split (50:50) between spring and summer, across soils with a range of soil pH values from a previous liming trial. The effect of soil pH ranges and P treatment rates on seasonal herbage growth and herbage P concentration was investigated over three years. Soil nutrient status was also investigated. Soil pH had a significant impact on the rate of mineralization and soil P concentration across each site. A soil pH of 6.2 caused a 1.8 mg/l increase in soil test P. An annual P application was necessary to maintain sufficient herbage P concentration for animal dietary requirements (0.35% DM), however there was no effect of P application or liming rate on herbage productivity across the three sites as all sites possessed sufficient soil P reserves. The current experiment has shown that despite optimal soil fertility status, ensuring sufficient plant available P is a problem on these particular soils.

The episode of widespread organic carbon deposition marked by peak black shale sedimentation during the Palaeoproterozoic is also reflected in exceptionally abundant graphite deposits of this age. Worldwide anoxic/euxinic sediments were preserved as a deep crustal reservoir of both organic carbon, and sulphur in accompanying pyrite, both commonly >1 wt %. The carbon- and sulphur-rich Palaeoproterozoic crust interacted with mafic magma to cause Ni–Co–Cu–PGE mineralization over the next billion years, and much uranium currently produced is from Mesoproterozoic deposits nucleated upon older Palaeoproterozoic graphite. Palaeoproterozoic carbon deposition has thus left a unique legacy of both graphite deposits and long-term ore deposition.

The recently developed fluorite (U–Th)/He thermochronology (FHe) technique was applied to date fluorite mineralization and elucidate the exhumation history of the Mazandaran Fluorspar Mining District (MFMD) located in the east Central Alborz Mountains, Iran. A total of 32 fluorite single-crystal samples from four Middle Triassic carbonate-hosted fluorite deposits were dated. The presented FHe ages range between c. 85 Ma (age of fluorite mineralization) and c. 20 Ma (erosional cooling during the exhumation of the Alborz Mountains). The Late Cretaceous FHe ages (i.e. 84.5 ± 3.6, 78.8 ± 4.4 and 72.3 ± 3.5 Ma) are interpreted as the age of mineralization and confirm an epigenetic origin for ore mineralization in the MFMD, likely a result of prolonged hydrothermal circulation of basinal brines through potential source rocks. Most FHe ages scatter around the Eocene Epoch (55.4 ± 3.9 to 33.1 ± 1.7 Ma), recording an important cooling event after heating by regional magmatism in an extensional tectonic regime. Cooling of the heated fluorites, as a result of thermal relaxation in response to geothermal gradient re-equilibration after the end of magmatism, or exhumation cooling during extensional tectonics characterized by lower amount of erosion are most probably the causes of the recorded Eocene FHe cooling ages. Oligocene–Miocene FHe ages (i.e. 27.6 ± 1.4 to 19.5 ± 1.1 Ma) are related to the accelerated uplift of the whole Alborz Mountains, possibly as a result of the initial collision between the Afro-Arabian and Eurasian plates further to the south.

The skeleton is the main site of P and Ca deposition; therefore, accurate estimation of Ca and P requirements is necessary to maintaining health and optimum performance of broiler chickens. A response surface methodology (RSM) using a central composite design (CCD) was used for evaluating and optimizing of Ca and non-phytate P (NPP) requirements of broiler chickens for optimal performance, ileal nutrient digestibility and bone mineralization from 1 to 21 days of age. A total of 750 one-day-old male broiler chickens (Ross 308) were randomly distributed into 50 cages including 9 treatments, each replicated 5 times (except central treatment with 10 replicates) and 15 birds in each cage by CCD. The dietary Ca levels of 4.3, 5.6, 8.6, 11.7 and 13.0 g/kg and NPP of 2.5, 2.9, 4.0, 5.0 and 5.4 g/kg were used for nine treatments of CCD. The results indicated that the linear and quadratic effects of NPP, quadratic effects of Ca and Ca × NPP were significant for average weight gain (AWG, P < 0.05), average feed intake (AFI, P < 0.05), feed conversion ratio (FCR, P < 0.05) and Ca and P apparent ileal digestibility (AID, P < 0.05); however, the linear effect of Ca was significant only for FCR (P < 0.05). On the other hand, tibia and toe ash were affected by NPP (linear and quadratic, P < 0.01) and Ca (quadratic, P < 0.01). The second-order polynomial regression model was significant for AWG (R2 = 0.93, P < 0.001), AFI (R2 = 0.88, P < 0.001), FCR (R2 = 0.78, P < 0.001), AID of Ca (R2 = 0.78, P < 0.001) and P (R2 = 0.88, P < 0.001), tibia ash (R2 = 0.86, P < 0.001) and toe ash (R2 = 0.85, P < 0.001). The multi-objective optimization indicated that broiler chickens from 1 to 21 days of age need 7.03 and 4.47 g/kg of Ca and NPP, respectively, to achieve optimal AWG, FCR, tibia and toe ash. However, the dietary Ca and NPP levels can be reduced to 6.57 and 3.95 g/kg with a slight negative impact on performance and bone mineralization, respectively. In conclusion, the findings indicate that using multi-objective optimization model such as RSM provides more information regarding optimum Ca and NPP requirements of broiler chickens, considering the complex interaction between these two minerals. While the NPP levels are in line with current recommended requirements, Ca levels are considerably lower and suggest that current recommended Ca requirements may be in excess of the needs of the broiler.

As distinctive spontaneous polarization and far-infrared radiation characteristics, the natural mineral tourmaline (TM) has the regulatory effect on crystallization behavior, which possesses potential application in biomimetic mineralization and bone regeneration. In this study, polyurethane (PU) and gelatin (GE) membranes with different adding proportion of TM nanoparticles were prepared via electrospinning. Additionally, the effect of TM nanoparticles on the mineralization process of hydrophobic PU and hydrophilic GE was investigated by immersing the composite TM/PU and TM/GE electrospun membranes in the 10× simulated body fluid (10SBF) at 37 °C for varying periods of time. SEM images confirmed the well-dispersed TM nanoparticles in the PU and GE electrospun fibers. The mineralization deposition was characterized by the SEM, EDS, XRD, and FTIR, and it indicated that two types of calcium phosphate deposits with different Ca/P molar ratios were obtained when TM/PU membranes and TM/GE membranes were incubated in 10SBF. Honeycomb-like hydroxyapatite crystals nucleated and grew faster on TM/PU and TM/GE membranes than the pure PU and GE membranes, respectively. Furthermore, with the increase of the added TM nanoparticles in the composite membranes, more calcium phosphate crystals were precipitated. These results showed that the added TM nanoparticles were able to improve the mineralization of polymer fibrous membranes, which is potential for the composite bone scaffold.

Gold mineralization at the Ashanti Mine occurs in shear zones which are second-order components of a major transcrustal shear zone. However, gold-rich telluride mineralization in veins in the hangingwall of the Obuasi ore zone at Ashanti appears to have post-dated development of the major gold-bearing shear zone. Complex assemblages of goethite, chalcocite, coloradoite, calaverite, sylvanite, kostovite, petzite, stutzite, hessite, altaite, rickardite, weissite and henryite were succeeded by a relatively simple assemblage of altaite-petzite-hessite ± sylvanite ± coloradoite. Precipitation occurred over a temperature range of approximately 220°C to 165°C from a CO2-bearing, low salinity (<5 wt. % NaCl equiv.) fluid under conditions of high ƒo2 and high ƒTe2/ƒS2. Replacement of earlier gold-sulphide mineralization is indicated.

The fluids were introduced during late activation of the Obuasi shear zone, which evolved during the c.2000 Ma Eburnean tectonothermal event that marked the onset of cratonization of the West African shield. The localized and time-specific distribution of the telluride mineralization may be indicative of a late influx of tellurium-rich fluid linked to emplacement of a synorogenic, Cape Coast-type granitoid intrusion.

X-ray computed tomography augmented by elemental microanalysis has been used to characterize two drill cores from the Borrowdale Volcanic Group, west Cumbria, UK. Information about the three-dimensional (3D) distribution of mineral phases was obtained non-destructively, and regionsof interest were extracted for thin sectioning and elemental analysis. This revealed the presence of pyrite and other iron- and iron-titanium-bearing minerals. X-ray computed tomography is a very useful tool for 3D visualization, but the limitations of the tomography system used made it difficultto distinguish between regions with similar compositions, such as the different layers within the calcite veins. Methods by which these limitations might be overcome are briefly discussed.

Surface and subsurface soils are complex biological, chemical, and physical environments and to understand the fate of pesticides in the soil environment is a formidable task. To determine the environmental fate of pesticides requires a diverse array of techniques and procedures. Microbiological approaches range from applied to basic, laboratory to field, qualitative to quantitative, and from low to high technology. In the arena of biodegradation, teams of scientists are needed to develop predictive models for the behavior of pesticides in the soil environment. From our perspectives, we have documented the existing status of the microbiology of environmental fate studies with pesticides. Verification of data from laboratory studies to the field environment is needed. On the other hand, efforts to design better field studies to assess microbial processes are essential to advance our understanding of environmental fate studies with pesticides.

Most well-drained Mississippi Delta soils have been used for cotton production, but corn has recently become a desirable alternative crop, and subsequently, atrazine use has increased. Between 2000 and 2001, 21 surface soils (0 to 5 cm depth) with known management histories were collected from various sites in Leflore, Sunflower, and Washington counties of Mississippi. Atrazine degradation was assessed in 30-d laboratory studies using 14C-ring–labeled herbicide. Mineralization was extensive in all soils with a history of one to three atrazine applications with cumulative mineralization over 30 d ranging from 45 to 72%. In contrast, cumulative mineralization of atrazine from three soils with no atrazine history was only 5 to 10%. However, one soil with no history of atrazine application mineralized 54 and 29% of the atrazine in soils collected in 2000 and 2001, respectively. Methanol extracted 15 to 23% of the 14C-atrazine 7 d after treatment in soils having two applications within the past 6 yr, whereas 65 to 70% was extracted from no-history soils. First-order kinetic models indicated soil with 2 yr of atrazine exposure exhibited a half-life of less than 6 d. Most probable number (MPN) estimates of atrazine-ring mineralizing-microorganisms ranged from 450 to 7,200 propagules g−1 in atrazine-exposed soils, and none were detected in soils with no history of atrazine use. Although most soils exhibited rapid atrazine mineralization, analysis of DNA isolated from these soils by direct or nested polymerase chain reaction (PCR) failed to amplify DNA sequences with primers for the atzA atrazine chlorohydrolase gene. These results indicate that microbial populations capable of accelerated atrazine degradation have developed in Mississippi Delta soils. This may reduce the weed control efficacy of atrazine but also reduce the potential for off-site movement. Studies are continuing to identify the genetic basis of atrazine degradation in these soils.

A field study was conducted on an s-triazine–adapted soil to determine the effects of s-triazine exclusion interval (1, 2, 3, or 4 yr), crop production system (continuous corn or continuous soybean), and rhizosphere proximity (bulk or rhizosphere soil) on atrazine degrader populations and activity. Atrazine degrader populations were quantified by a radiological Most Probable Number technique, while degrader activity was assessed via mineralization of ring-labeled 14C-atrazine. As the s-triazine exclusion interval increased, atrazine degrader populations declined exponentially, regardless of crop or rhizosphere proximity. Crop and exclusion interval interacted to affect degrader populations (P = 0.0043). Pooled over rhizosphere and bulk soil, degrader populations were 1.5-fold higher and declined 2.8-fold faster in soybean than corn. An interaction between rhizosphere proximity and exclusion interval was also noted (P = 0.0021), whereby degrader populations were 1.9-fold higher and declined 2.8-fold slower in rhizosphere compared with bulk soil, regardless of crop. The time required for 50% mineralization of ring-labeled 14C-atrazine (DT50) following exclusion of s-triazine herbicides increased linearly at a rate of 2.2 d yr−1. In contrast, the DT50 for this site prior to a known s-triazine application was 85 d and declined exponentially over 5 yr of successive atrazine applications: 24.5 d after 1 yr, 10.8 d after two successive years, and 3.8 d after five successive atrazine applications. Omitting s-triazines can reduce degrader populations and activity in adapted soils, but more than 4 yr is required to return mineralization kinetics to nonadapted levels, regardless of crop or rhizosphere proximity.

Drained coastal peatlands are a source of greenhouse gas (GHG) through abundant CO2 release caused by aerobic peat degradation. Published rates of CO2 fixation and CH4 release for natural peatlands suggest that areas of peat formation are a (small) net source of GHG emission because the radiative effect of emitted CH4 exceeds the CO2 uptake by the vegetation. It is shown here that wetland restoration of reclaimed peat areas in the western Netherlands leads to a reduction of GHG emission because the expected increase in anaerobically generated CH4 release is much smaller than the decrease in aerobically produced CO2.

Dentinogenesis imperfecta type II (DGI-II) lacks intrafibrillar mineral with severe compromise of dentin mechanical properties. A Dspp knockout (Dspp–/–) mouse, with a phenotype similar to that of human DGI-II, was used to determine if poly-L-aspartic acid [poly(ASP)] in the “polymer-induced liquid-precursor” (PILP) system can restore its mechanical properties. Dentin from six-week old Dspp–/– and wild-type mice was treated with CaP solution containing poly(ASP) for up to 14 days. Elastic modulus and hardness before and after treatment were correlated with mineralization from Micro x-ray computed tomography (Micro-XCT). Transmission electron microscopy (TEM)/Selected area electron diffraction (SAED) were used to compare matrix mineralization and crystallography. Mechanical properties of the Dspp–/– dentin were significantly less than wild-type dentin and recovered significantly (P < 0.05) after PILP-treatment, reaching values comparable to wild-type dentin. Micro-XCT showed mineral recovery similar to wild-type dentin after PILP-treatment. TEM/SAED showed repair of patchy mineralization and complete mineralization of defective dentin. This approach may lead to new strategies for hard tissue repair.

This study investigated the effects of mistletoe infection on N cycling in a semi–arid savanna, south-west Zimbabwe. We established five plots (10 × 10 m) which each included three large canopy-dominant Acacia karroo trees infected by one of three mistletoes (Erianthemum ngamicum, Plicosepalus kalachariensis and Viscum verrucosum) and non-infected A. karroo trees. In each plot, we measured litterfall, litter quality (N, phenolics, tannins and lignin), soil nutrient concentrations and N transformations beneath tree canopies. Soil N, P and Ca were greatest beneath trees infected by P. kalachariensis than beneath non-infected trees. Litterfall and litter N returns were 1.5, 2 and 1.4 times more beneath A. karroo trees infected by E. ngamicum, P. kalachariensis and V. verrucosum, respectively. Mineral N increased with mistletoe infection but did not exceed 20%. Soil N transformations were greater beneath trees infected by E. ngamicum (> 40%), and lower beneath trees infected by P. kalachariensis (<50%) and V. verrucosum (<48%) than beneath non-infected A. karroo trees. Soil N transformations were negatively correlated with condensed tannins, lignin and lignin : N. We conclude that the improved N concentration can increase resource heterogeneity, which may alter the ecosystem structure and functioning in the semi-arid savanna.

Data on litterfall, litter layers accumulated on top of the mineral soil and layer mineralization collected for three years in a tropical rain forest at Pernambuco, Brazil, were implemented on a simulation model. Litterfall was collected biweekly using 11 collectors 1 × 1 m. Every three months, 20 litter mat samples, 0.5 × 0.5 m, were collected, divided into the L, F and H layers and the CO2 evolution from each litter layer was determined in the laboratory. Litterfall, in the three years, averaged 7.8, 8.3 and 8.2 Mg ha-1 y-1, most of it leaves. Litter mat masses varied widely from place to place (15–90 Mg ha-1) and the overall averages were 5.6, 7.6 and 26.1 Mg ha-1 for the L, F and H layers, with CO2 evolution averages of 2.27, 0.507 and 0.123 mgC g litter C-1 day-1. According to the model, the L layer had a high turnover rate, losing 4.7 Mg ha-1 y-1 through mineralization and 3.4 Mg ha-1 y-1 transferred to the F layer. Values for the F and H layers were 1.4 and 1.2 mineralized and 2.0 and 0.8 Mg ha-1 y-1 transferred. Thus, it would take 2.1, 6.7 and 39 years for newly fallen leaves to be mostly fragments, to be transformed to humus and to be incorporated to the soil organic matter, respectively. Variations of litterfall throughout the three years would have little effect on the system which was not very sensitive to litterfall changes, except for the top layer.

There is a perception that sustained frequent fires cause nitrogen limitation over the long term (50–100 y) by volatilizing the nitrogen in soil, plant biomass and litter. Here we test this perception in a South African savanna located in the Kruger National Park. At our study site we compare the effects of 50 y of fire exclusion, season (August and February) and frequency (triennial and annual August and triennial February) of burn on nitrogen cycling and availability. We do this using three different methods to determine nitrogen mineralization; in situ incubations, laboratory incubations and ion-exchange resin bags. On each treatment we established two parallel transects 100 m apart with 10 sampling points per treatment along these transects. Daily mineralization rates for in situ incubations were determined monthly from August 2004 to June 2005 at each of the sampling points. Ion-exchange resin bags were buried (5 cm) at the same points and left in the field from August 2004 to August 2005. In February 2005 five randomly located soil samples from each of the four treatments were collected for laboratory incubations using a 7-cm-diameter soil auger. Regardless of method used our results show that there are no significant differences in daily nitrogen mineralization rates after 50 y of different burning treatments from annual burning to fire exclusion. In fact, both in situ and laboratory incubations show that nitrogen availability is higher on the annual burn than the fire exclusion (0.16 μg g−1 soil d−1 vs. 0.11 μg g−1 soil d−1 and 0.46 μg g−1 soil d−1 vs. 0.30 μg g−1 soil d−1 respectively). Perceived negative effects of fire on ecosystem functioning has curbed the use of fire as a management tool with fire often actively suppressed in savanna. The results of our study show that fire can be used more vigorously in mesic African savanna to manipulate tree:grass ratios without negatively affecting the nitrogen cycle.