An environmental magnetic study, sedimentological and numerical methods around Tauranga Harbour, New Zealand

Magnetic iron minerals are widespread and indicative sediment constituents in estuarine, coastal and shelf systems. We combine environmental magnetic, sedimentological and numerical methods to identify magnetite-enriched placer-like zones in a complex coastal system and delineate their formation mechanisms. Magnetic susceptibility and remanence measurements on 245 surficial sediment samples collected in and around Tauranga Harbour, the largest barrier-enclosed tidal estuary of New Zealand, reveal several discrete enrichment zones controlled by local hydrodynamic conditions. Active magnetite enrichment takes place in tidal channels, which feed into two coast-parallel nearshore magnetite-enriched belts centered at water depths of 6-10 m and 10-20 m. A close correlation between magnetite content and magnetic grain size was found, where higher susceptibility values are associated within coarser magnetic crystal sizes. Two key mechanisms for magnetite enrichment are identified. First, tide-induced residual currents primarily enable magnetite enrichment within the estuarine channel network. A coast-parallel, fine sand magnetite enrichment belt in water depths of less than 10 m along the barrier island has a strong decrease in magnetite content away from the southern tidal inlet and is apparently related to active coast-parallel transport combined with mobilizing surf zone processes. A second, less pronounced, but more uniform magnetite enrichment belt at 10-20 m water depth is composed of non-mobile, medium-coarse-grained relict sands, which have been reworked during post-glacial sea level transgression. We demonstrate the potential of magnetic methods to reveal and differentiate coastal magnetite enrichment patterns and investigate their formative mechanisms.

Analysis of biogenic magnetite nanoparticles

Cobalt doped magnetite (CoxFe3-xO4) nanoparticles have been produced through the microbial reduction of cobalt-iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by SQUID, x-ray magnetic circular dichroism, Mössbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to <4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe2+ site with Co2+, with up to 17 per cent Co substituted into tetrahedral sites.

Petrology and geochemistry of oceanic intraplate sheet-flow basalts at DSDP Hole 89-462A

Reentry of Hole 462A during Leg 89 resulted in the penetration of a further 140 m of basalt sheet-flows similar to those found during Leg 61 at the same site. Twelve volcanic units (45 to 56) were recognized, comprising a series of rapidly extruded, interlayered aphyric and poorly clinopyroxene-plagioclase-olivine phyric, nonvesicular basalts. All exhibit variable, mild hydration and oxidation, relative to fresh oceanic basalts, produced under reducing, low-CO2-activity conditions within the zeolite facies. Secondary assemblages are dominated by smectites, zeolites, and pyrite, produced by low-temperature reaction with poorly oxygenated seawater. No systematic mineralogical or chemical changes are observed with depth, although thin quenched units and more massive hypocrystalline units exhibit slightly different alteration parageneses. Chemically, the basalts are olivine- and quartz-normative tholeiites, characterized by low incompatible-element abundances, similar to mildly enriched MORB (approaching T-type), with moderate, chrondite-normalized, large-ionlithophile- element depletion patterns and generally lower or near-chrondritic ratios for many low-distribution-coefficient (KD) element pairs. In general, relative to cyclic MORB chemical variation, they are uniform throughout, although 3 chemical megagroups and 22 subgroups are recognized. It is considered that the megagroups represent separate low-pressure-fractionated systems (olivine + Plagioclase ± clinopyroxene), whereas minor variations within them (subgroups) indicate magma mixing and generation of near-steady-state conditions. Overall, relatively minor fractionation coupled with magma mixing produced a series of compositionally uniform lavas. Parental melts were produced by similar degrees of partial melting, although the source may have varied slightly in LIL-element content.

Geochemistry at DSDP Leg 82 Holes

DSDP Leg 82 drilled nine sites to the southwest of the Azores Islands on the west flank of the Mid-Atlantic Ridge (MAR) in an attempt to determine the temporal and spatial evolution of the Azores "hot-spot" activity. The chemistry of the basalts recovered during Leg 82 is extremely varied: in Holes 558 and 561, both enriched (E-type: CeN/YbN = 1.5 to 2.7; Zr/Nb = 4.5 to 9.6) and depleted (or normal-N-type: CeN/YbN = 0.6 to 0.8; Zr/Nb > 20) mid-ocean ridge basalts (MORB) occur as intercalated lava flows. To the north of the Hayes Fracture Zone, there is little apparent systematic relationship between basalt chemistry and geographic position. However, to the south of the Hayes Fracture Zone, the chemical character of the basalts (N-type MORB) is more uniform. The coexistence of both E-type and N-type MORB in one hole may be explicable in terms of either complex melting/ fractionation processes during basalt genesis or chemically heterogeneous mantle sources. Significant variation in the ratios of strongly incompatible trace elements (e.g., La/Ta; Th/Ta) in the basalts of Holes 558 and 561 are not easily explicable by processes such as dynamic partial melting or open system crystal fractionation. Rather, the trace element data require that the basalts are ultimately derived from at least two chemically distinct mantle sources. The results from Leg 82 are equivocal in terms of the evolution of the Azores "hot spot," but would appear not to be compatible with a simple model of E-type MORB magmatism associated with upwelling mantle "blobs." Models that invoke a locally chemically heterogeneous mantle are best able to account for the small-scale variation in basalt chemistry.

Electromagnetic, rock magnetic, and geochemical properties of surficial sediments in Eckernförde Bay

Submarine groundwater discharge in coastal settings can massively modify the hydraulic and geochemical conditions of the seafloor. Resulting local anomalies in the morphology and physical properties of surface sediments are usually explored with seismo-acoustic imaging techniques. Controlled source electromagnetic imaging offers an innovative dual approach to seep characterization by its ability to detect pore-water electrical conductivity, hence salinity, as well as sediment magnetic susceptibility, hence preservation or diagenetic alteration of iron oxides. The newly developed electromagnetic (EM) profiler Neridis II successfully realized this concept for a first time with a high-resolution survey of freshwater seeps in Eckernförde Bay (SW Baltic Sea). We demonstrate that EM profiling, complemented and validated by acoustic as well as sample-based rock magnetic and geochemical methods, can create a crisp and revealing fingerprint image of freshwater seepage and related reductive alteration of near-surface sediments. Our findings imply that (1) freshwater penetrates the pore space of Holocene mud sediments by both diffuse and focused advection, (2) pockmarks are marked by focused freshwater seepage, underlying sand highs, reduced mud thickness, higher porosity, fining of grain size, and anoxic conditions, (3) depletion of Fe oxides, especially magnetite, is more pervasive within pockmarks due to higher concentrations of organic and sulfidic reaction partners, and (4) freshwater advection reduces sediment magnetic susceptibility by a combination of pore-water injection (dilution) and magnetite reduction (depletion). The conductivity vs. susceptibility biplot resolves subtle lateral litho- and hydrofacies variations.

Geochemistry of marin ash layers and epiclastic rocks from the Kerguelen Plateau

Epiclastic volcanogenic rocks recovered from the Kerguelen Plateau during Ocean Drilling Program Legs 119 and 120 comprise (pre-)Cenomanian(?) claystones (52 m thick, Site 750); a Turonian(?) basaltic pebble conglomerate (1.2 m thick, Site 748; Danian mass flows (45 m thick, Site 747); and volcanogenic debris flows of Quaternary age at Site 736 (clastic apron of Kerguelen Island). Pyroclastic rocks comprise numerous Oligocene to Quaternary marine ash layers. The epiclastic sediments with transitional mid-ocean-ridge basalt (T-MORB) origin indicate weathering (Site 750) and erosion (Site 747) of Early Cretaceous T-MORB from a then-emergent Kerguelen Plateau, connected to Late Cretaceous tectonic events. The basal pebble conglomerate of Site 748 has an oceanic-island basalt (OIB) composition and denotes erosion and reworking of seamount to oceanic-island-type volcanic sources. The vitric- to crystal-rich marine ash layers are a few centimeters thick, have rather uniform grain sizes around 60 ± 40 µm, and are a result of Plinian eruptions. Crystal-poor silicic vitric ashes may also represent co-ignimbrite ashes. The ash layers have bimodal, basaltic, and silicic compositions with a few intermediate shards. The basaltic ashes are evolved high-titanium T-MORB; a few grains in a silicic pumice lapilli layer have a low-titanium basaltic composition. The silicic ashes comprise trachytic and rhyolitic glass shards belonging to a high-K series, except for a few low-K glasses admixed to a basaltic ash layer. Feldspar and clinopyroxene compositions fit the glass chemistry: high-Ti tholeiite-basaltic glasses have Plagioclase of An40-80 and pigeonite to augite clinopyroxene compositions. Silicic ashes have K-rich anorthoclase and minor Plagioclase around An20 and ferriaugitic to hedenbergitic clinopyroxene compositions. The line of magmatic evolution for the glass shards is not compatible with simple two-end member (high-Ti T-MORB and high-K rhyolite) mixing, but favors successive Ca-Mg-Fe pyroxene, Ti magnetite, and apatite fractionation, and K-rich alkali feldspar fractionation in trachytic magmas to yield rhyolitic compositions. Plagioclase fractionation occurs throughout. This qualitative model is in basic accordance with the observed mineral assemblage. However, as the time span for explosive volcanism spans >30 m.y., this basic model cannot comply with fractional crystallization in a single magma reservoir. The ash layers resulted from highly explosive eruptions on Kerguelen and, with less probability, Heard islands since the Oligocene. The explosive history starts with widespread Oligocene basaltic ash layers that indicate sea-level or subaerial volcanism on the Northern Kerguelen Plateau. After a hiatus of 24 m.y.(?), explosive magmatic activity was vigorously renewed in the late Miocene with more silicic eruptions. A peak in explosive activity is inferred for the Pliocene-Pleistocene. The composition and evolution of Kerguelen Plateau ash layers resemble those from other hotspot-induced, oceanic-island realms such as Iceland and Jan Mayen in the North Atlantic, and the Canary Islands archipelago in the Central Atlantic.

Geochemistry and minerals at DSDP Hole 76-534A

Leg 76 sampled 31.5 m of basaltic basement at Deep Sea Drilling Project Hole 534A in the Blake-Bahama Basin. The basalts represent a short section of mineralogically uniform, sparsely plagioclase-phyric pillow flows, composed mainly of plagioclase, augitic clinopyroxene, iron-titanium oxides with variable amounts of alteration products (smectite ± carbonate ± quartz). Their major element chemistry is typical of mid-ocean ridge tholeiites and has normative compositions of olivine tholeiites. Mg/(Mg + Fe**2+) ratios range from 0.58 to 0.60, which suggests that these basalts are evolved compared to primitive mantle melts.

Scaling up the production of biogenic magnetite nanoparticles

Although there are numerous examples of large-scale commercial microbial synthesis routes for organic bioproducts, few studies have addressed the obvious potential for microbial systems to produce inorganic functional biomaterials at scale. Here we address this by focusing on the production of nano-scale biomagnetite particles by the Fe(III)-reducing bacterium Geobacter sulfurreducens, which was scaled-up successfully from lab-scale to pilot plant-scale production, whilst maintaining the surface reactivity and magnetic properties which make this material well suited to commercial exploitation. At the largest scale tested, the bacterium was grown in a 50 L bioreactor, harvested and then inoculated into a buffer solution containing Fe(III)-oxyhydroxide and an electron donor and mediator, which promoted the formation of magnetite in under 24 hours. This procedure was capable of producing up to 120 g biomagnetite. The particle size distribution was maintained between 10 and 15 nm during scale-up of this second step from 10 ml to 10 L, with conserved magnetic properties and surface reactivity; the latter demonstrated by the reduction of Cr(VI). The process presented provides an environmentally benign route to magnetite production and serves as an alternative to harsher synthetic techniques, with the clear potential to be used to produce kg to tonne quantities.

(Table 1) Percentage of non-opaque heavy minerals, heavy residue, magnetite, and opaque heavy minerals, DSDP Sites 58-445 and 58-446

Heavy-mineral analyses were made for 39 samples, 27 from DSDP Site 445 and 12 from Site 446. About one-fourth of the samples were so loose that they were easily disaggregated in water. The amount of heavy residue and the magnetite content of the heavy fraction were very high, 0.2 to 44 per cent and (on the average) more than 20 per cent, respectively. Among the non-opaque heavy minerals, common hornblende (0 to 80%) and augite (0 to 98%) are most abundant. Pale-green and bluish-green amphiboles (around 10%) and the epidote group (a few to 48%) are next in abundance. Euhedral apatite and biotite and irregularly shaped chromite are not abundant, but are present throughout the sequence. Hacksaw structure is developed in pale-green amphibole and augite. At Site 445, a fair amount of chlorite and a few glauconite(?) grains are present from Core 445-81 downward. The content of common hornblende and opaque minerals also changes from Core 445-81 downward. A geological boundary may exist between Cores 445-77 and 445-81. Source rocks of the sediments at both sites were basaltic volcanic rocks (possibly alkali suite), schists, and ultramafic rocks. The degree of lithification and amount of heavy residue, and the content of magnetite, non-opaque heavy minerals (excluding mafic minerals), and mafic minerals in the cores were compared with Eocene, Oligocene, and Miocene sandstones of southwest Japan. In many respects, the sediments at Sites 445 and 446 are quite different from those of southwest Japan. From the early Eocene to the early Miocene, the area of these sites belonged to a different geologic province than southwest Japan.