Mineralogy of selected geological deposits from the United Kingdom and the Republic of Ireland as possible capping materials for low-level radioactive waste disposal facilities

Solid low-level radioactive waste (LLW) is currently being disposed at a number of facilities in the United Kingdom (UK). The safety of these facilities relies to some extent on the use of engineered barriers, such as a cap, to isolate the waste and protect the environment. Generally, the material used as the barrier layer within such a cap should be of low permeability and it should retain this property over long timescales (beyond a few decades normally required for facilities containing non-radioactive wastes). The objective of this research is to determine the mineralogy of selected geological deposits from the UK and Ireland as part of a larger project to examine their suitability as a capping material, particularly on LLW sites. Mineral transformations, as a result of future climate change, may impact on the long-term performance of the cap and even the disposal facility. X-ray diffraction (XRD) was carried-out on the sand, silt and clay fractions of the London Clay, Belfast Upper Boulder Clay, Irish Glacial Till, Belfast Sleech, and Ampthill Clay geological deposits. Minerals were present that could pose both positive and negative effects on the long-term performance of the cap. Smectite, which has a high shrink swell potential, may produce cracks in London Clay, Belfast Upper Boulder Clay and Ampthill Clay capping material during dry, hotter periods as a possible consequence of future climate change; thus, resulting in higher permeability. Ampthill Clay and Belfast Sleech had elevated amounts of organic matter (OM) at 5.93% and 5.88%, respectively, which may also contribute to cracking. Over time, this OM may decompose and result in increased permeability. Gypsum (CaSO4) in the silt and sand fractions of Ampthill Clay may reduce the impact of erosion during wetter periods if it is incorporated into the upper portion of the cap. There are potential negative effects from the acidity created by the weathering of pyrite (FeS2) present in the silt and sand fractions of Belfast Sleech and Ampthill Clay that could impede the growth of grasses used to stabilize the surface of the capping material if this material is used as part of the vegetative soil layer. Additionally, acidic waters generated from pyrite weathering could negatively impact the lower lying capping layers and the disposal facility in general. However, the calcium carbonate (CaCO3) present in the silt and sand fractions of these deposits, and dolomite (CaMg(CO3)2) in Belfast Sleech, may counter act the acidity.

Detection of Mixing Dynamics During Pumping of a Flooded Coal Mine

In complex hydrogeological environments the effective management of groundwater quality problems by pump-and-treat operations can be most confidently achieved if the mixing dynamics induced within the aquifer by pumping are well understood. The utility of isotopic environmental tracers (C-, H-, O-, S-stable isotopic analyses and age indicators—14C, 3H) for this purpose is illustrated by the analysis of a pumping test in an abstraction borehole drilled into flooded, abandoned coal mineworkings at Deerplay (Lancashire, UK). Interpretation of the isotope data was undertaken conjunctively with that of major ion hydrochemistry, and interpreted in the context of the particular hydraulic setting of flooded mineworkings to identify the sources and mixing of water qualities in the groundwater system. Initial pumping showed breakdown of initial water quality stratification in the borehole, and gave evidence for distinctive isotopic signatures (d34S(SO4) ~= -1.6‰, d18O(SO4) ~= +15‰) associated with primary oxidation of pyrite in the zone of water table fluctuation—the first time this phenomenon has been successfully characterized by these isotopes in a flooded mine system. The overall aim of the test pumping—to replace an uncontrolled outflow from a mine entrance in an inconvenient location with a pumped discharge on a site where treatment could be provided—was swiftly achieved. Environmental tracing data illustrated the benefits of pumping as little as possible to attain this aim, as higher rates of pumping induced in-mixing of poorer quality waters from more distant old workings, and/or renewed pyrite oxidation in the shallow subsurface.

After the Aznalcóllar mine spill:arsenic, zinc, selenium, lead and copper levels in the livers and bones of five waterfowl species

In April 1998, a holding lagoon containing pyrite ore processing waste, failed and released 5-6 million m3 of highly polluting sludge and acidic water. Over 2650 ha of the internationally important Doñana Natural Park became contaminated, along with <100 ha of the more pristine Doñana National Park. In order to assess the affect of the spill on waterfowl from Doñana, bone and liver samples from 124 individuals have been analysed for As, Pb, Cu, Zn and Se. Five species have been studied, from the Rallidae (rails), Anatini (dabbling ducks) and Aythyini (pochards) families. Geometric mean bone concentrations 2-3 months after the spill were in the order of Zn > Cu > Pb > Se > As, while liver concentrations were in the order of Zn > Cu > Se > Pb > As. Dry weight bone concentrations ranged from n.d-1.76 mg kg(-1) As, 109.4-247.6 mg kg(-1) Zn, 0.06-1.27 mg kg(-1) Se, n.d-134.11 mg kg(-1) Pb, and 2.18-8.92 mg kg(-1) Cu. Wet weight liver concentrations ranged from n.d-0.34 mg kg(-1) As, 29.8-220.1 mg kg(-1) Zn, 0.15-0.85 mg kg(-1) Se, n.d-3.80 mg kg(-1) Pb, and 7.30-742.96 mg kg(-1) Cu. The most important factor related to the accumulation of these metals was commonly species; however, location and sex also had important effects on liver As levels, location and age affected Cu levels, while Zn and Pb were affected by age, sex and location. Birds from Natural Park areas were found to have significantly higher levels of bone Zn, Pb and Cu, and liver As and Cu than birds from National Park areas. Female birds had higher liver As, Zn and Pb than males; whilst adults appeared to have lower bone As and Zn but higher liver Pb than chicks/juveniles. Although metal concentrations were elevated in certain individuals, in the majority of birds studied, they did not reach levels widely considered to be toxic. However, it would appear that As and Cu liver levels (which may be indicative of short-medium term pollutant exposure) were elevated in waterbirds which died in the spill contaminated Natural Park, 2-3 months after the disaster.

Arsenic levels in the soils and macrophytes of the 'Entremuros' after the Aznalcóllar mine spill

In April 1998, a holding lagoon containing pyrite ore processing waste rich in arsenic, failed and released 5-6 million m(3) of highly polluting sludge and acidic water. Over 2700 ha of the internationally important Doñana National and Natural Parks were contaminated. The area of Natural Park to sustain the greatest impact was known as the Entremuros. This paper presents 0-5 cm soil monitoring data from the Entremuros, from sampling campaigns 6 and 18 months after the disaster; as well as macrophyte root, rhizome and stem data from samples taken 18 months after the spill. Results show a clear, decreasing, north-south arsenic soil pollution trend, both 6 and 18 months after the spill, and suggest a small reduction in total soil arsenic levels occurred over time; although a significant increase in extractable arsenic is also noted. The two macrophytes (Typha dominguensis and Scirpus maritimus) studied herein are not accumulating arsenic in stem parts, however, accumulation of arsenic on iron plaque on the roots of these plants may be occurring. Further work is recommended in order to determine the ecotoxicological significance of this process in relation to the avian food-chains of Doñana, and elsewhere.

The distribution of arsenic in soils affected by the Aznalcóllar mine spill, SW Spain

In April 1998, a holding lagoon containing pyrite ore processing waste, failed and released an estimated 5-6 million m(3) of metal rich sludge and acidic waters into the Rio Guadiamar, SW Spain. Over 2700 ha of the internationally important Doñana National and Natural Parks were contaminated. The sludge component of the waste contained up to 0.6% arsenic. This paper presents an extensive set of 0-5 cm soil analyses results from samples taken 6-8 months after the spill. Data are presented on pseudo-total arsenic levels in these samples, and on arsenic removed by both single batch and sequential extraction techniques. Pseudo-total levels of arsenic in the sludge ranged from 1521 to 3510 mg kg(-1), and a mean 4.4% of this was found to be extractable using 2.5% acetic acid. Soils in the Guadiamar Valley and Entremuros areas (those worst affected by the spill) were found to contain 85.4-782 mg kg(-1) and 7.1-196 mg kg(-1) pseudo-total arsenic, respectively. The mean acetic acid extractable component in these areas was 2.5% and 4.9%, respectively. Background pseudo-total arsenic levels in the soils of the area have been found to be 4.2-13.6 mg kg(-1). Rapid input of acidic waters, and the acidic nature of the sludge itself, may have caused depletion of Mg, Na and K, and to a lesser extent Mn, Ca and PO(4) in the upper 5 cm of the worst affected soils. Sequential extraction results suggest clear As-Fe associations, and possible As-Mn associations within the more soluble phases.

Diagenetic Alterations and Reservoir Quality Evolution of Lower Cretaceous Fluvial Sandstones: Nubian Formation, Sirt Basin, North-Central Libya

Lower Cretaceous meandering and braided fluvial sandstones of the Nubian Formation form some of the most important subsurface reservoir rocks in the Sirt Basin, north-central Libya. Mineralogical, petrographical and geochemical analyses of sandstone samples from well BB6-59, Sarir oilfield, indicate that the meandering fluvial sandstones are fine- to very fine-grained subarkosic arenites (av. Q91F5L4), and that braided fluvial sandstones are medium- to very coarse-grained quartz arenites (av. Q96F3L1). The reservoir qualities of these sandstones were modified during both eodiagenesis (ca. <70oC; <2 km) and mesodiagenesis (ca. >70oC; >2km). Reservoir quality evolution was controlled primarily by the dissolution and kaolinitization of feldspars, micas and mud intraclasts during eodiagenesis, and by the amount and thicknessof grain-coating clays, chemical compaction and quartz overgrowths during mesodiagenesis. However, dissolution and kaolinitization of feldspars, micas and mud intraclasts resulted in the creation of intercrystalline micro- and mouldic macro-porosity and permeability during eodiagenesis, which were more widespread in braided fluvial than in meandering fluvial sandstones. This was because of the greater depositional porosity and permeability in the braided fluvial sandstones which enhanced percolation of meteoric waters. The development of only limited quartz overgrowths in the braided fluvial sandstones, in which quartz grains are coated by thick illite layers, retained high porosity and permeability (12-23 % and 30- 600 mD). By contrast, meandering fluvial sandstones underwent porosity loss as a result of quartz overgrowth development on quartz grains which lack or have thin and incomplete grain-coating illite (2-15 % and 0-0.1mD). Further loss of porosity in the meandering fluvial sandstones occurred as a result of chemical compaction (pressuredissolution) induced by the occurrence of micas along grains contacts. Otherdiagenetic alterations, such as the growth of pyrite, siderite, dolomite/ankerite and albitization, had little impact on reservoir quality. The albitization of feldspars may have had minor positive influence on reservoir quality throughthe creation of intercrystalline micro-porosity between albite crystals.The results of this study show that diagenetic modifications of the braided and meandering fluvial sandstones in the Nubian Formation, and resulting changes in reservoir quality, are closely linked to depositional porosity and permeability. They are also linked to the thickness of grain-coating infiltrated clays, and to variations in detrital composition, particularly the amounts of mud intraclasts, feldspars and mica grains as well as climatic conditions.

Sequence stratigraphy related distribution of diagenetic alterations In Miocene deltaic and shoreface arenites, the Suez Rift, EGYPT.

The distribution of eogenetic alterations in shoreface-offshore and coarse-grained deltaic, calcarenite to hybrid arenites of the Mheiherrat Formation (lower Rudeis), Early Miocene, the Gulf of Suez, Egypt) can be constrained within a sequence stratigraphic framework. The bioclast-rich, shoreface (trangressive systems tract; TST) and shoreface (highstand systems tract; HST) arenites, particularly those below the parasequence boundaries and maximum flooding surface, are cemented by grain-coating microcrystalline, circumgranular isopacheous acicular and columnar, and coarse-crystalline calcite (δ18OVPDB = -3.6 to -0.3 ‰; δ13CVPDB = -2.3 to -0.7 ‰), non-Ferro an dolomite (δ18OVPDB = -3.9 to +0.9‰; δ13CVPDB = -2.5 ‰ to -0.7 ‰), and pyrite. Zeolite, palygorskite and gypsum occur in the HST shoreface arenites, being enhanced by aird climatic condations. The coarse-grained deltaic LST deposits are pervasively cemented by coarse-crystalline, pore-filling calcite and small amounts of microcrystalline calcite (δ18OVPDB = -4.4 to -2.3 ‰; δ13CVPDB = -2.8 to -1.3 ‰) and non-ferroan dolomite (δ18OVPDB = -4.8 to -2.5 ‰; δ13CVPDB = -3.3 to -1.5 ‰). Thus, this study demonstrates that changes in pore-water chemistry, which induced changes in the texture, composition and extent of cementation in the Miocene arenites was controlled by changes in the relative sea level and by the paleo-climatic conditions during deposition of the HST arenites.

Sequence stratigraphy related distribution of diagenetic alterations In Miocene deltaic and shoreface arenites, the Suez Rift, EGYPT.. Available from: https://www.researchgate.net/publication/264545153_Sequence_stratigraphy_related_distribution_of_diagenetic_alterations_In_Miocene_deltaic_and_shoreface_arenites_the_Suez_Rift_EGYPT [accessed Apr 15, 2015].

Joint inversion of magnetotelluric and seismic data for crustal characterization

Tese de doutoramento, Ciências Geofísicas e da Geoinformação (Geofisíca), Universidade de Lisboa, Faculdade de Ciências, 2014

Genesis of the brecciated rocks from mid atlantic ridge hydrothermal systems : Lucky Strike (37º50’N) and Menez Gwen (37º50’N)

Tese de doutoramento, Geologia (Metalogenia), Universidade de Lisboa, Faculdade de Ciências, 2014

The role of a transcrustal shear zone in orogenic gold mineralization at the Aijanahalli Mine, Dharwar Craton, South India

The Ajjanahalli gold mine is spatially associated with a Late Archean craton-scale shear zone in the eastern Chitradurga greenstone belt of the Dharwar craton, India. Gold mineralization is hosted by an similar to100-m-wide antiform in a banded iron formation. Original magnetite and siderite are replaced by a peak metamorphic alteration assemblage of chlorite, stilpnomelane, minnesotaite, sericite, ankerite, arsenopyrite, pyrite, pyrrhotite, and gold at ca. 300degrees to 350degreesC. Elements enriched in the banded iron formation include Ca, Mg, C, S, An, As, Bi. Cu, Sb, Zn, Pb, Se, Ag, and Te, whereas in the wall rocks As, Cu, Zn, Bi, Ag, and An are only slightly enriched. Strontium correlates with CaO, MgO, CO2, and As, which indicates cogenetic formation of arsenopyrite and Mg-Ca carbonates. The greater extent of alteration in the Fe-rich banded iron formation layers than in the wall rock reflects the greater reactivity of the banded iron formation layers. The ore fluids, as interpreted from their isotopic composition (delta(18)O = 6.5-8.5parts per thousand; initial Sr-87/Sr-86 = 0.7068-0.7078), formed by metamorphic devolatilization of deeper levels of the Chitradurga greenstone belt. Arsenopyrite, chalcopyrite, and pyrrhotite have delta(34)S values within a narrow range between 2.1 and 2.7 per mil, consistent with a sulfur source in Chitradurga greenstone belt lithologies. Based on spatial and temporal relationships between mineralization, local structure development, and sinistral strike-slip deformation in the shear zone at the eastern contact of the Chitradurga greenstone belt, we suggest that the Ajjanahalli gold mineralization formed by fluid infiltration into a low strain area within the first-order structure. The ore fluids were transported along this shear zone into relatively shallow crustal levels during lateral terrane accretion and a change from thrust to transcurrent tectonics. Based on this model of fluid flow, exploration should focus on similar low strain areas or potentially connected higher order splays of the first-order shear zone.

Pizgrischite, (Cu,Fe)Cu14PbBi17S35, a new sulfosalt from the Swiss Alps: Description, crystal structure and occurrence

Pizgrischite, (Cu,Fe)Cu14PbBi17S35, is a new mineral species named after the type locality, Piz Grisch Mountain, Val Ferrera, Graubunden, Switzerland. This sulfosalt occurs as thin, striated, metallic lead-grey blades measuring up to I cm in length, embedded in quartz and associated with tetrahedrite, chalcopyrite, pyrite, sphalerite, emplectite and derivatives of the aikinite-bismuthinite series. In plane-polarized light, the new species is brownish grey with no perceptible pleochroism; under crossed nicols in oil immersion, it presents a weak anisotropy with dark brown tints. Minimum and maximum reflectance values (in %) in air are: 40.7-42.15 (470 nm), 41.2-43.1 (546 nm), 41.2-43.35 (589 nm) and 40.7-43.3 (650 nm). Cleavage is perfect along 001 I and well developed on {010}. Abundant polysynthetic twinning is observed on (010). The mean micro-indentation hardness is 190 kg/mm(2) (Mohs hardness 3.3), and the calculated density is 6.58 g/cm(3). Electron-microprobe analyses yield (wt%; mean result of seven analyses): Cu 16.48, Pb 2.10, Fe 0.77, Bi 60.70, Sb 0.35, S 19.16, Se 0.04, total 99.60. The resulting empirical chemical formula is (Cu15.24Fe0.80Pb0.60)(Sigma 16.64)(Bi17.07Sb0.17)(Sigma 17.24)(S35.09Se0.03)(Sigma 35.12), in accordance with the formula derived from the single-crystal refinement of the structure, (Cu,Fe)Cu14PbBi17S35. Pizgrischite is monoclinic, space group C2/m, with the following unit-cell parameters: a 35.054(2), b3.91123(I), c43.192(2) angstrom, beta 96.713(4)degrees, V5881.24 angstrom(3), Z=4. The strongest seven X-ray powder-diffraction lines [d in angstrom (I)(hkl)] are: 5.364(40)((6) over bar 04), 4.080(50)((8) over bar 05), 3.120(40)(118), 3.104(68)((3) over bar 18), 2.759(53) ((9) over bar 11),2.752(44)(910) and 1.956(100)(020). The crystal structure is an expanded monoclinic derivative of kupcikite. Pizgrischite belongs to the cuprobismutite series of bismuth sulfosalts but, sensu stricto, it is not a homologue of cuprobismutite. At the type locality. pizarischite is the result of the Alpine metamorphism under greenschist-facies conditions of pre-Tertiary hydrothermal Cu-Bi mineralization.

Stable hydrogen and oxygen isotope composition of waters from mine tailings in different climatic environments

The stable isotope composition of waters (delta H-2, delta O-18) can be used as a natural tracer of hydrologic processes in systems affected by acid mine drainage. We investigated the delta H-2 and delta O-18 values of pore waters from four oxidizing sulfidic mine tailings impoundments in different climatic regions of Chile (Piuquenes at La Andina with Alpine climate, Cauquenes and Caren at El Teniente with Mediterranean climate, and Talabre at the Chuquicamata deposit with hyperarid climate). No clear relationship was found between altitude and isotopic composition. The observed displacement of the tailings pore waters from the local meteoric water line toward higher delta O-18 values (by similar to +2% delta O-18 relative to delta H-2) is partly due to water-rock interaction processes, including hydration and O-isotope exchange with sulfates and Fe(III) oxyhydroxides produced by pyrite oxidation. In most tailings, from the saturated zone toward the surface, isotopically different zones can be distinguished. Zone I is characterized by an upward depletion of H-2 and O-18 in the pore waters from the saturated zone and the lowermost vadose zone, due to ascending diffused isotopically light water triggered by the constant loss of water vapor by evaporation at the surface. In zone II, the capillary flow of a mix of vapor and liquid water causes an evaporative isotopic enrichment in H-2 and O-18. At the top of the tailings in dry climate a zone III between the capillary zone and the surface contains isotopically light diffused and atmospheric water vapor. In temperate climates, the upper part of the profile is affected by recent rainfall and zone III may not differ isotopically from zone II.

Geology of the Sand Creek porphyry molybdenum prospect /

The Sand Creek Prospect is located within the eastern exposed margin of the Coast Plutonic Complex. The occurrence is a plug and dyke porphyry molybdenum deposit. The rock types, listed in decreasing age: 1) metamorphlc schists and gneisses; 2) diorite suite rocks - diorite, quartz diorite, tonalite; 3) rocks of andesitic composition; 4) granodiorites, coarse porphyritic granodiorite, quartzfeldspar porphyry, feldspar porphyry; and 5) lamprophyre. Hydrothermal alteration is known to have resulted from emplacement of the hornblende-feldspar porphyry through to the quartz-feldspar porphyry. Molybdenum mineralization is chiefly associated with the quartz-feldspar porphyry. Ore mineralogy is dominated by pyrite with subordinate molybdenite, chalcopyrite, covelline, sphalerite, galena, scheelite, cassiterite and wolframite. Molybdenite exhibits a textural gradation outward from the quartz-feldspar porphyry. That is, disseminated rosettes and rosettes in quartz veins to fine-grained molybdenite in quartz veins and potassic altered fractures to fine-grained molybdenite paint or 6mears in the peripheral zones. The quartz-feldspar porphyry dykes were emplaced in an inhomogeneous stress field. The trend of dykes, faults and shear zones is 0^1° to 063° and dips between 58° NW and 86* SE. Joint Pole distribution reflects this fault orientation. These late deformatior maxima are probably superimposed upon annuli representing diapiric emplacement of the plutons. A model of emplacement involving two magmatic pulses is given in the following sequence: Diorite pulse (i) dioritequartz diorite, (ii) tonalites; granodiorite pulse (iii) hornblende-fildspar microporphyry, hornblende/biotite porphyry, (iv) coarse grained granodiorite, (v) quartz-feldspar porphyry, (vi) feldspar porphyry, and (vii) lamprophyre. The combination of plutonic and coarse porphyritic textures, extensive propylitic overprinting of potassic alteration assemblages suggests that the. prospect represents the lower reaches of a porphyry system.

Genesis and distribution of Mississippi Valley-type ore assemblages in Middle Silurian strata, Niagara Peninsula, Ontario /

Presently non-commercial occurrences of Mississippi Valley-type ore assemblages in the Middle Silurian strata of the Niagara Peninsula have been studied. Based on this detailed study, a new poly-stage genetic model is proposed which relates ore mineralization in carbonate environments to the evolution of the sedimentary basin. Sulphide ore mineralization occurred during two episodes: 1. During the late diagenesis stage, which is characterized by compaction-maturation of the sediments, the initial mineralization took place by upward and outward movement of connate waters. Metals were probably supplied from all the sediments regardless of their specific lithologies. However, clay minerals were possibly the main contributors. The possible source of sulphur was from petroleum-type hydrocarbons presently mixed with the sediments at the site of ore deposition. Evidence for this is the fact that the greatest abundance of ore minerals is in petroliferous carbonates. The hydrocarbons probably represent liquids remaining after upward migration to the overlying Guelph-Salina reservoirs. The majority of sphalerite and galena formed during this period, as well as accessory pyrite, marcasite, chalcopyrite, chalcocite, arsenopyrite, and pyrrhotite; and secondary dolomite, calcite, celestite, and gypsum. 2. During the presently ongoing surface erosion and weathering phase, which is marked by the downward movement of groundwater, preexisting sulphides were probably remobilized, and trace amounts of lead and zinc were leached from the host material, by groundwaters. Metal sulphides precipitated at, or below, the water table, or where atmospheric oxygen could raise the Eh of groundwaters to the point where soluble metal complexes are unstable and native sulphur co-precipitates with sphalerite and galena. This process, which can be observed today, also results in the transport and deposition of the host rock material. Breakdown of pre-existing sulphide and sulphate, as well as hydrocarbon present in the host rock, provided sulphur necessary for sulphide precipitation. The galena and sphalerite are accompanied by dolomite, calcite, gypsum, anglesite, native sulphur and possibly zincite.

Microstructural and geochemical investigation of North American lower-middle Paleozoic trilobites and recent arthropods

Trilobites ¥tere collected from Ordovician and Devonian formations of Ontario} New York} Ohio} Oklahoma} and Indiana. Diversity was generally low} but 19..?telllS and Ph..~tY>ps ¥tere the most abundant species from the Ordovician and Devonian} respectively. Recent marine arthropods ¥tere collected from the Atlantic shore of the middle Florida Keys} and from the Pacific and lagoonal waters at Cape Beale} B. C. Fresh-water arthropods were collected along the shore of the Severn River in northcentral Ontario. Cuticles ¥tere analyzed for major} minor and trace elements, 180 and 13C isotopes, as ¥tell as examined by scanning electron micr?scope to identify original and diagenetic fabrics. Examination of trilobite cuticles by scanning electron microscope revealed several microstructures consistent with those observed in Recent arthropods. Microstructures} such as setae and tegumental gland duct openings} in like sized Lim/IllS and Isoteline trilobites may indicate common ancestral origins for these organisms, or simply parallel cuticle evolutions. The dendritic microstructure, originally' thought to be a diagenetic indicator, was found in Recent specimens and therefore its presence in trilobites may be suggestive of the delicate nature of diagenesis in trilobites. The absence of other primary microstructures in trilobites may indicate alteration, taxonomic control} or that there is some inherent feature of S EM examination which may' not allow detection of some features} while others are apparently visit·le onl~1 under SH.·1. The region of the cuticle sampled for examination is also a major influence in detecting pristine microstructures, as not all areas of trilobite and Recent arthropod cuticles will have microstructures identifiable in a SEM study. Subtleties in the process of alteration, however} ma~·· leave pristine microstructures in cuticles that are partial~/ silicified or do 10m itized, and degree and type of alteration may vary stratigraphically and longitudinally within a unit. The presence of fused matrices, angular calcite rhombs, and pyrite in the cuticle are thought to be indicative of altered cuticles, although pyritization may not affect the entire cuticle. t-~atural processes in Recent arthropods, such as molting, lead to variations in cuticle chemistries, and are thought to reflect the area of concentration of the elements during calcification. The level of sodium in Recent arthropods was found to be higher than that in trilobites, but highly mobile when sUbjected to the actions of VY'€'athering. Less saline water produced lovy'€'r magnesium and higher calcium values in Recent specimens .. and metal variations in pristine Ordovician trilobite cuticle appears to follow the constraints outlined for Recent arthropods, of regulation due to the chemislry of the surrounding medium. In diagenetic analysis, sodium, strontium and magnesium proved most beneficial in separating altered from least altered trilobites. Using this criterion, specimens from shale show the least amount of geochemical alteration, and have an original mineralogy of 1.7 - 2.4 mole % MgC03 (8000 t(> 9500 ppm magnesium) for both /s>..?/e/11S lJA'i.riff!11S and PseIAit'11J17ites I..itmirpin..itl/~ and 2.8 - 3.3 mole % MgC03 (5000 to 7000 ppm magnesium) for Ph.i{).?PS This is Slightly lower than the mineralogy of Recent marine arthropods (4.43 - 12.1 mole % MgC03), and slightly higher than that of fresh-water crayfish (0.96 - 1.82 mole % MgC03). Geochemically pristine trilobites were also found to possess primary microstructures. Stable isotope values and trends support the assertion that marine-meteoriclburial fluids were responsible for the alteration observed in a number of the trilobite specimens. The results of this stUdy suggest that fossil material has to be evaluated separately along taxonomic and lithological lines to arrive at sensible diagenetic and e nvironmenta I interpretations.