Toxic Cyanobacteria in Greek Freshwaters, 1987—2000: Occurrence,Toxicity, and Impacts in the Mediterranean Region

In a survey in Greece from 1987 to 2000 hepatotoxic cyanobacterial blooms were observed in 9 out of 33 freshwaters. Microcystins (MCYSTs) were detected by HPLC in 7 of these lakes, and the total MCYST concentration per scum dry weight ranged from 50.3 to 1638 ± 464 μg g^—1. Cyanobacterial genera (Microcystis, Anabaena, Anabaenopsis, Aphanizomenon, Cylindrospermopsis) with known toxin producing taxa were present in 31 freshwaters. From our data and a review of the literature, it would appear that Mediterranean countries are more likely 1) to have toxic cyanobacterial blooms consisting of Microcystis spp. and 2) to have higher intracellular MCYST concentrations. A case study in Lake Kastoria is used to highlight seasonal patterns of cyanobacterial and MCYST‐LR occurrence and to assess cyanotoxin risk. Cyanobacterial biovolume was high (> 11 μL L^—1) throughout the year and was in excess of Guidance Level 2 (10 μL L^—1) proposed by WHO for recreational waters and Alert Level 2 for drinking water. Further, surface water samples from April to November exceeded Guidance Level 3, with the potential for acute cyanobacterial poisoning. Intracellular MCYST‐LR concentrations (max 3186 μg L^—1) exceeded the WHO guideline for drinking water (1 μg L^—1) from September to November with a high risk of adverse health effects. Preliminary evidence indicates that in 3 lakes microcystins are accumulated in some aquatic organisms. Generally, a high risk level can be deduced from the data for the Mediterranean region.     

Soft X-ray spectroscopic studies of the reaction of fractured pyrite surfaces with Cr(VI)-containing aqueous solutions

We have used synchrotron-based soft X-ray core-level photoemission and adsorption spectroscopies to study the reaction of aqueous sodium chromate solutions with freshly fractured pyrite surfaces. Pyrite surfaces were reacted with 50 μM sodium chromate solution at pH 7 for reaction times between 1 min and 37 hr. Additional experiments were performed at pH 2 and pH 4 with 50 μM sodium chromate solutions and at pH 7 with 5 mM solutions. At chromate concentrations of 50 μM, all chromium present on the pyrite surface was in the form of Cr(III), while at 5 mM, both Cr(III) and Cr(VI) were present at the pyrite surface. Minor quantities of oxidized sulfur species (sulfate, sulfite, and zero-valent sulfur) were identified as reaction products on the pyrite surface. The amount of oxidized sulfur species observed on the surface was greater when pyrite was reacted with 5 mM Cr(VI) solutions because the rate of chromium deposition exceeded the rate of dissolution of pyrite oxidation products, effectively trapping Cr(VI) and oxidized sulfur species in an overlayer of iron(III)-containing Cr(III)-hydroxide. This work shows that pyrite, an extremely cheap and readily available waste material, may be suitable for the removal of hexavalent chromium from acidic to circumneutral waste streams. The reduced chromium ultimately forms a coating on the pyrite surface, which passivates the pyrite surface towards further oxidation.     

Laboratory and case studies of thermal cycling and stored strain on the stability of selected marbles

Studies of marble panels from the exterior of two buildings document the processes leading to bowing of the material. Bowing of panels is most extensive in those areas that are exposed to direct or reflected thermal energy. The thermal anisotropic behavior of calcite results in grain-boundary separation, grain sliding and microfracturing. The resulting loss of strength is one factor leading to bowing. The development of bows further reduces the panel strength as the outer portions elongate by inelastic deformation mechanisms. Laboratory experiments cycling marble samples for over 200 cycles at three temperatures up to 107°C above room conditions show similar strength losses as the natural situation. The second factor contributing to the bowing process is the release of residual elastic strain. The strain is in part stored in the marble from its geologic history, but may also be accumulated during thermal cycling due to the properties of calcite. Marble panels have been found to bow when stored outside, but not attached to any framework, indicating that the release of residual strain is a critical factor in producing the bows.     

Lu–Hf and U–Pb isotope systematics of zircons from the Storgangen intrusion, Rogaland Intrusive Complex, SW Norway: implications for the composition and evolution of Precambrian lower crust in the Baltic Shield

The Storgangen orebody is a concordantly layered, sill-like body of ilmenite-rich norite, intruding anorthosites of the Rogaland Intrusive Complex (RIC), SW Norway. 17 zircon grains were separated from ca. 5 kg of sand-size flotation waste collected from the on-site repository from ilmenite mining. These zircons were analysed for major and trace elements by electron microprobe, and for U–Pb and Lu–Hf isotopes by laser ablation microprobe plasma source mass spectrometry. Eight of the zircons define a well-constrained (MSWD=0.37) concordant population with an age of 949±7 Ma, which is significantly older than the 920–930 Ma ages previously reported for zircon inclusions in orthopyroxene megacrysts from the RIC. The remaining zircons, interpreted as inherited grains, show a range of ²⁰⁷Pb/²⁰⁶Pb ages up to 1407±14 Ma, with an upper intercept age at ca. 1520 Ma. The concordant zircons have similar trace element patterns, and a mean initial Hf isotope composition of ¹⁷⁶Hf/¹⁷⁷Hf_{949 Ma}=0.28223±5 (_Hf=+2±2). This is similar to the Hf-isotope composition of zircons in a range of post-tectonic Sveconorwegian granites from South Norway, and slightly more radiogenic than expected for mid-Proterozoic juvenile crust. The older, inherited zircons show Lu–Hf crustal residence ages in the range 1.85–2.04 Ga. One (undated) zircon plots well within the field of Hf isotope evolution of Paleoproterozoic rocks of the Baltic Shield. These findings indicate the presence of Paleoproterozoic components in the deep crust of the Rogaland area, but do not demonstrate that such rocks, or a Sveconorwegian mantle-derived component, contributed significantly to the petrogenesis of the RIC. If the parent magma was derived from a homogeneous, lower crustal mafic granulite source, the lower crustal protolith must be at least 1.5 Ga old, and it must have an elevated Rb/Sr ratio. This component would be indistinguishable in Sr, Nd and Hf isotopes from some intermediate mixtures between Sveconorwegian mantle and Paleoprotoerzoic felsic crust, but it cannot account for the initial ¹⁴³Nd/¹⁴⁴Nd of the most primitive, late Sveconorwegian granite in the region, without the addition of mantle-derived material.     

The geology of kimberlite pipes of the Ekati property, Northwest Territories, Canada

This paper reviews key characteristics of kimberlites on the Ekati property, NWT, Canada. To date 150 kimberlites have been discovered on the property, five of which are mined for diamonds. The kimberlites intrude Archean basement of the central Slave craton. Numerous Proterozoic diabase dykes intrude the area. The Precambrian rocks are overlain by Quaternary glacial sediments. No Phanerozoic rocks are present. However, mudstone xenoliths and disaggregated sediment within the kimberlites indicate that late-Cretaceous and Tertiary cover (likely <200 m) was present at the time of emplacement. The Ekati kimberlites range in age from 45 to 75 Ma. They are mostly small pipe-like bodies (surface area mostly <3 ha but up to 20 ha) that typically extend to projected depths of 400–600 m below current surface. Pipe morphologies are strongly controlled by joints and faults. The kimberlites consist primarily of variably bedded volcaniclastic kimberlite (VK). This is dominated by juvenile constituents (olivine and lesser kimberlitic ash) and variable amounts of exotic sediment (primarily mud), with minor amounts of xenolithic wall-rock material (generally <5%). Kimberlite types include: mud-rich resedimented VK (mRVK); olivine-rich VK (oVK); sedimentary kimberlite; primary VK (PVK); tuffisitic kimberlite (TK) and magmatic kimberlite (MK). The presence and arrangement of these rock types varies widely. The majority of bodies are dominated by oVK and mRVK, but PVK is prominent in the lower portions of certain kimberlites. TK is rare. MK occurs primarily as precursor dykes but, in a few cases, forms pipe-filling intrusions. The internal geology of the kimberlites ranges from simple single-phase pipes (RVK or MK), to complex bodies with multiple, distinct units of VK. The latter include pipes infilled with steep, irregular VK blocks/wedges and at least one case in which the pipe is occupied by well-defined sub-horizontal VK phases, including a unique, 100-m-thick graded sequence. The whole-rock compositions of VK samples suggest significant loss of kimberlitic fines during eruption followed by variable dilution by surface sediment and concurrent incorporation of kimberlitic ash. Diamond distribution within the kimberlites reflects the amount and nature of mantle material sampled by individual kimberlite phases, but is modified considerably by eruption and depositional processes. The characteristics of the Ekati kimberlites are consistent with a two-stage emplacement process: (1) explosive eruption/s causing vent clearing followed by formation of a significant tephra rim/cone of highly fragmented, olivine-enriched juvenile material with varying amounts of kimberlitic ash and surface sediments (predominantly mud); and (2) infilling of the vent by direct deposition from the eruption column and/or resedimentation of crater rim materials. The presence of less fragmented, juvenile-rich PVK in the lower portions of certain pipes and the intrusion of large volumes of MK to shallow levels in some bodies suggest emplacement of relatively volatile-depleted, less explosive kimberlite in the later stages of pipe formation and/or filling. Explosive devolatilisation of CO₂-rich kimberlite magma is interpreted to have been the dominant eruption mechanism, but phreatomagmatism is thought to have played a role and, in certain cases, may have been dominant.     

Inclusions in diamonds from the K14 and K10 kimberlites, Buffalo Hills, Alberta, Canada: diamond growth in a plume?

Analyses of mineral inclusions, carbon isotopes, nitrogen contents and nitrogen aggregation states in 29 diamonds from two Buffalo Hills kimberlites in northern Alberta, Canada were conducted. From 25 inclusion bearing diamonds, the following paragenetic abundances were found: peridotitic (48%), eclogitic (32%), eclogitic/websteritic (8%), websteritic (4%), ultradeep? (4%) and unknown (4%). Diamonds containing mineral inclusions of ferropericlase, and mixed eclogitic-asthenospheric-websteritic and eclogitic-websteritic mineral associations suggests the possibility of diamond growth over a range of depths and in a variety of mantle environments (lithosphere, asthenosphere and possibly lower mantle).

Eclogitic diamonds have a broad range of C-isotopic composition (δ¹³C=−21‰ to −5‰). Peridotitic, websteritic and ultradeep diamonds have typical mantle C-isotope values (δ¹³C=−4.9‰ av.), except for two ¹³C-depleted peridotitic (δ¹³C=−11.8‰, −14.6‰) and one ¹³C-depleted websteritic diamond (δ¹³C=−11.9‰). Infrared spectra from 29 diamonds identified two diamond groups: 75% are nitrogen-free (Type II) or have fully aggregated nitrogen defects (Type IaB) with platelet degradation and low to moderate nitrogen contents (av. 330 ppm-N); 25% have lower nitrogen aggregation states and higher nitrogen contents (30% IaB; <1600 ppm-N).

The combined evidence suggests two generations of diamond growth. Type II and Type IaB diamonds with ultradeep, peridotitic, eclogitic and websteritic inclusions crystallised from eclogitic and peridotitic rocks while moving in a dynamic environment from the asthenosphere and possibly the lower mantle to the base of the lithosphere. Mechanisms for diamond movement through the mantle could be by mantle convection, or an ascending plume. The interaction of partial melts with eclogitic and peridotitic lithologies may have produced the intermediate websteritic inclusion compositions, and can explain diamonds of mixed parageneses, and the overlap in C-isotope values between parageneses. Strong deformation and extremely high nitrogen aggregation states in some diamonds may indicate high mantle storage temperatures and strain in the diamond growth environment. A second diamond group, with Type IaA–IaB nitrogen aggregation and peridotitic inclusions, crystallised at the base of the cratonic lithosphere. All diamonds were subsequently sampled by kimberlites and transported to the Earth's surface.     

Genesis and evolution of the lithospheric mantle beneath the Buffalo Head Terrane, Alberta (Canada)

Mantle xenoliths and xenocrysts were retrieved from three of the 88–86 Ma Buffalo Hills kimberlites (K6, K11, K14) for a reconnaissance study of the subcontinental lithospheric mantle (SCLM) beneath the Buffalo Head Terrane (Alberta, Canada). The xenoliths include spinel lherzolites, one garnet spinel lherzolite, garnet harzburgites, one sheared garnet lherzolite and pyroxenites. Pyroxenitic and wehrlitic garnet xenocrysts are derived primarily from the shallow mantle and lherzolitic garnet xenocrysts from the deep mantle. Harzburgite with Ca-saturated garnets is concentrated in a layer between 135–165 km depth. Garnet xenocrysts define a model conductive paleogeotherm corresponding to a heat flow of 38–39 mW/m². The sheared garnet lherzolite lies on an inflection of this geotherm and may constrain the depth of the lithosphere–asthenosphere boundary (LAB) beneath this region to ca 180 km depth.

A loss of >20% partial melt is recorded by spinel lherzolites and up to 60% by the garnet harzburgites, which may be related to lithosphere formation. The mantle was subsequently modified during at least two metasomatic events. An older metasomatic event is evident in incompatible-element enrichments in homogeneous equilibrated garnet and clinopyroxene. Silicate melt metasomatism predominated in the deep lithosphere and led to enrichments in the HFSE with minor enrichments in LREE. Metasomatism by small-volume volatile-rich melts, such as carbonatite, appears to have been more important in the shallow lithosphere and led to enrichments in LREE with minor enrichments in HFSE. An intermediate metasomatic style, possibly a signature of volatile-rich silicate melts, is also recognised. These metasomatic styles may be related through modification of a single melt during progressive interaction with the mantle. This metasomatism is suggested to have occurred during Paleoproterozoic rifting of the Buffalo Head Terrane from the neighbouring Rae Province and may be responsible for the evolution of some samples toward unradiogenic Nd and Hf isotopic compositions.

Disturbed Re–Os isotope systematics, evident in implausible model ages, were obtained in situ for sulfides in several spinel lherzolites and suggest that many sulfides are secondary (metasomatic) or mixtures of primary and secondary sulfides. Sulfide in one peridotite has unradiogenic ¹⁸⁷Os/¹⁸⁸Os and gives a model age of 1.89±0.38 Ga. This age coincides with the inferred emplacement of mafic sheets in the crust and suggests that the melts parental to the intrusions interacted with the lithospheric mantle.

A younger metasomatic event is indicated by the occurrence of sulfide-rich melt patches, unequilibrated mineral compositions and overgrowths on spinel that are Ti-, Cr- and Fe-rich but Zn-poor. Subsequent cooling is recorded by fine exsolution lamellae in the pyroxenes and by arrested mineral reactions.

If the lithosphere beneath the Buffalo Head Terrane was formed in the Archaean, any unambiguous signatures of this ancient origin may have been obliterated during these multiple events.