The distribution of trace metals in the western North Atlantic off Nova Scotia

The distributions of Fe, Mn, Zn, Cu, Ni, Cd and Co have been determined in a section across the Scotian Shelf into the Atlantic Slope water. Significant differences in concentration exist for most of the trace metals between the four water masses in the section. Depletions of trace metal concentration in the highly productive Atlantic Slope water relative to the underlying Central Atlantic water are thought to be due to biological activity.The distributions of Fe and Mn are strongly related to the distribution of suspended particulate matter. The concentrations of Fe and Mn, extracted from the suspended matter on the Scotian Shelf, are considerably higher than those in the non-detrital fraction of the underlying sediments. This suggests that post-depositional changes cause the loss of both elements from the non-detrital fraction of the particles. Whereas Mn shows major nearshore increases in concentration related to continental runoff, nearshore Fe concentrations are largely controlled by particulate matter distribution. Continental runoff does not appear to have much influence upon the distributions of the other trace metals.     

Sensitivity of coastal waters to anthropogenic trace metal emissions

Trace metal concentrations in the waters of the Gulf of St. Lawrence and the Scotian Shelf and their sensitivity to changes in the composition of the major contributor of fresh water, the St. Lawrence River, are assessed. Comparison of the levels of trace metals in eastern Canadian coastal waters with those in other coastal waters of the world reveals that the former area generally has lower trace metal concentrations and is, therefore, probably less contaminated than elsewhere. The increased anthropogenic activity in the St. Lawrence drainage basin required to increase the levels of trace metals in receiving coastal waters by detectable amounts is discussed. We demonstrate that faster and more reliable warning of changes due to anthropogenic activity will be revealed through river monitoring than through monitoring of coastal waters. Changes in the marine environment can then be assessed through a thorough understanding of the geochemical behaviour of trace metals in nearshore waters.     

An intercalibration for trace metals in seawater

This paper describes the results of a recent international intercalibration experiment for trace metals in seawater. The results show that considerable improvements in analytical ability have been made for several metals at concentrations close to those found in offshore marine waters. Some systematic differences between the results of analyses of frozen and acidified samples are evident for most metals. The application of two different analytical techniques, atomic absorption spectrophotometry and anodic stripping voltammetry, appears to introduce relatively small differences in the results for copper and cadmium at near-natural concentrations.Two factors limiting our ability to conduct trace metal intercalibrations at the levels found in the deep ocean are the extent of tolerable contamination, especially for zinc and lead, and the degree to which the overall homogeneity of a group of intercalibration samples can be assured. Some reexamination of methods of sample preparation needs to be carried out before such low level calibrations can be effectively conducted.     

Manganese recycling in coastal waters

Both water and suspended particulate matter in the deep water of the Gulf of St. Lawrence are greatly enriched in manganese. Maximum dissolved manganese concentrations are encountered close to the sediment-water interface whereas the particulate matter with highest manganese content occurs 30–100 m above the bottom. The elevated concentrations are attributed to the diagenetic release of dissolved manganese from the underlying fine-grained sediments and its subsequent precipitation in the water column. The rate of manganese precipitation is rapid compared to the rates of diffusion and mixing in the bottom water. Part of the manganese-enriched particulate matter becomes mixed throughout the water column by advection and diffusion. Thus, particles enriched in manganese can ultimately be carried into the open ocean by prevailing currents. This process, which appears to be widespread in eastern Canadian coastal waters, enables manganese originally associated with rapidly settling terrigenous particles to be transferred to slowly settling fine-grained suspended particles entering the ocean from coastal environments. In this way, riverborne manganese of terrigenous origin may well account for a major proportion of the excess manganese in pelagic sediments.     

New data on the Indus Kohistan seismic zone and its extension into the Hazara–Kashmir Syntaxis, NW Himalayas of Pakistan

This paper deals with the data obtained from local networks in northern Pakistan for 251 earthquakes of magnitude ≥4.0 for October 8, 2005 to December 31, 2006 period. The study presents focal mechanism solutions (FMS) of 12 pre- (1904–2005) and 17 post- (October 8, 2005–December, 2005) Muzaffarabad Earthquake, their detailed tectonic interpretation, and correlation with surface evidence of co-seismic rupture with published synthetic aperture radar data. Distribution of landslides obtained from National Engineering Services of Pakistan and the earthquake damages are also discussed. Aftershock distribution, which is more prominent in the crystalline zone (northwest of Muzaffarabad), defines a 50-km-wide NW–SE trending zone that extends for 200 km from the main mantle thrust to the center of the Hazara–Kashmir Syntaxis. The FMS of the main shock and 16 aftershocks having magnitude ≥4.0 indicate thrusting to be the dominant mechanism with rupture planes having NW–SE trend and NE dip. In addition, 12 FMS of pre-Muzaffarabad Earthquake (1904–2004) from the same area have been determined and results are compared. This leads to the conclusion that the wedge-shaped NW–SE trending blind zone, referred to by earlier workers as the Indus Kohistan Seismic Zone (IKSZ), has been activated during the Muzaffarabad earthquake. The right-lateral component in all FMS, supported by the surface evidences, suggests the involvement of Balakot–Bagh Fault (BBF). We propose that the IKSZ is the source of the October 8, 2005 Muzaffarabad earthquake that reactivated the BBF. Furthermore, the IKSZ does not end at the nose of the syntaxis but extends further southeast of it. Tectonic complexity seems to be due to a variety of factors. Also, thrust and reverse solutions near the northern collisional boundary (main mantle thrust) have mostly NE/SW-directed P-axis orientations. From the detailed FMS analysis, three conclusions have been drawn: (1) Shallow events (depth ≤10 km) with prominent strike slip solutions (earlier earthquakes) are associated with the surface strike slip faults (e.g., Muzaffarabad Fault) and/or the Besham domal structure; (2) moderate depth events (depth 10–25 km) with thrust/reverse solutions but having minor right-lateral strike slip component (all Muzaffarabad earthquakes and two earlier) are associated with the IKSZ; (3) deeper earthquakes (depth below IKSZ) with pure thrust/reverse solutions may be related to the under-thrusting of the Indian plate beneath the IKSZ, which represents a major thrust zone. Imbricate thrusting and breaking and thickening of the crust are considered to be caused by steep bending of the under-thrusting plate at the collisional boundary. An erratum to this article can be found at     

Factors affecting seasonality of lithogenic and biogenic particle flux in a large estuarine ecosystem

Seasonal patterns of vertical flux over two years (2001–2003) at two stations in the Bras d'Or Lakes, a large estuary in Cape Breton Island, Nova Scotia, were determined using aluminum and organic carbon in settled particles collected in moored traps to calculate lithogenic (terrigenous) and marine biogenic fractions. On an annual basis, lithogenic material comprised 53% and 81% of dry weight and 48% and 66% of organic carbon in settled particles at the deep- (128 m) and shallow-water (41 m) locations, respectively. Peaks in runoff, inferred from rain and snowfall precipitation, ice cover and possible horizontal transport of resuspended sediment coincided with maximum sedimentation rates of lithogenic material during unstratified periods between October and March. Biological factors correlated with phytoplankton and ice algal primary production and seasonal changes in zooplankton grazing inferred from phaeopigments controlled biogenic particle fluxes under stratified conditions between June and September and during winter. Year-to-year variations in deposition of lithogenic and marine biogenic material depended on seasonal differences in stratification, precipitation, freeze/melt conditions and the extent of ice cover.     

VHMS mineralisation at Erayinia in the Eastern Goldfields Superterrane: Geology and geochemistry of the metamorphosed King Zn deposit

Despite having been a target for volcanic-hosted massive sulfide (VHMS) deposits since the 1960s, few resources have been defined in the Archean Yilgarn Craton of Western Australia. Exploration challenges associated with regolith and deep cover exacerbate the already-difficult task of exploring for small, deformed deposits in stratigraphically complex, metamorphosed volcanic terranes. We present results of drill-core logging, petrography, whole-rock geochemistry and portable X-ray Fluorescence data from the King Zn deposit, to help refine mineralogical and geochemical halos associated with VHMS mineralisation in amphibolite-facies greenstone sequences of the Yilgarn Craton. The King Zn deposit (2.15?Mt at 3.47?wt% Zn) occurs as a 1–7 m-thick stratiform lens dominated by iron sulfides, in an overturned, metamorphosed volcanic rock-dominated sequence located ～140?km east of Kalgoorlie. The local stratigraphy is characterised by garnet-amphibolite and strongly banded intermediate to felsic schists, with rare horizons of graphitic schist and talc schist. Massive sulfide mineralisation is characterised by stratiform pyrite–pyrrhotite–sphalerite at the contact between quartz–muscovite schists (‘the footwall dacite’), and banded quartz–biotite and amphibole?±?garnet schists of the stratigraphic hanging-wall. A zone of pyrite–(sphalerite) and pyrrhotite–pyrite–(chalcopyrite) veining extends throughout the stratigraphic footwall. Footwall garnet-amphibolites are of sub-alkaline basaltic affinity, with a central zone dominated by chlorite?±?magnetite interpreted to represent the Cu-bearing feeder zone. SiO₂, CaO, Fe₂O_3T, MgO and Cu concentrations are highly variable, reflecting quartz–epidote?±?chlorite?±?magnetite?±?sulfide alteration. Hydrothermal alteration in stratigraphically overlying intermediate to felsic rocks is characterised by a mineral assemblage of quartz–muscovite?±?chlorite?±?albite?±?carbonate. Cordierite and anthophyllite are locally significant and indicative of zones of Mg-metasomatism prior to metamorphism. Increases in SiO₂, Fe₂O_3T, pathfinder elements (e.g. As, Sb, Tl), and depletions of Na₂O, CaO, Sr and MgO occur in quartz–muscovite schists approaching massive sulfide mineralisation. Within all strata (including the immediate hanging-wall), the following pathfinder elements are strongly correlated with Zn: Ag, As, Au, Bi, Cd, Eu/Eu*, Hg, In, Ni, Pb, Sb, Se and Tl. These geochemical halos resemble less metamorphosed VHMS deposits across the Yilgarn Craton and suggest that although metamorphism leads to element mobility and mineral segregation at the thin-section scale, assay samples of ～20?cm length are sufficient to vector to mineralisation in amphibolite facies greenstone belts. Recognition of minerals such as Mg-chlorite, muscovite, cordierite, anthophyllite, biotite/phlogopite, and abundant garnet are significant, in addition to Al-rich phases (i.e. kyanite, sillimanite, andalusite and/or staurolite) not identified at King. Chemographic diagrams may be used to identify and distinguish different alteration trends, along with several alteration indices (e.g. Alteration Index, Carbonate–Chlorite–Pyrite Index, Silicification Index) and the abundance of normative corundum and quartz.     

Tracing the source of 3,3'-dichlorobiphenyl found in samples collected in and around Halifax Harbour

3,3'-dichlorobiphenyl (IUPAC No. 11), a chlorobiphenyl (CB) that is not generally analysed in environmental studies of CBs, is found, sometimes at high concentrations, in water, suspended particulate material, biota and sediments from Halifax Harbour, NS, Canada. The results presented demonstrate the need for investigations of non-Aroclor CBs like CB 11. Not only can they have rather elevated environmental concentrations like those reported here for CB 11, but they also can be members of the more toxic non-ortho class of CBs and thus important from a toxicity standpoint. The focus of this paper was to investigate the possible sources of CB 11, a trace constituent of commercial mixtures, but dominant in various environmental compartments of Halifax Harbour.     

Geological setting of the 8 October 2005 Kashmir earthquake

The source of the 8 October 2005 earthquake of M 7.6 was the northwest-striking Balakot–Bagh (B–B) fault, which had been mapped by the Geological Survey of Pakistan prior to the earthquake but had not been recognized as active except for a 16-km section near Muzaffarabad. The fault follows the Indus–Kohistan Seismic Zone (IKSZ); both cut across and locally offset the Hazara–Kashmir Syntaxis defined by the Main Boundary and Panjal thrusts. The fault has no expression in facies of the Miocene–Pleistocene Siwalik Group but does offset late Pleistocene terrace surfaces in Pakistan-administered Jammu-Kashmir. Two en-échelon anticlines near Muzaffarabad and Balakot expose Precambrian Muzaffarabad Limestone and are cut by the B–B fault on their southwest sides, suggesting that folding and exposure of Precambrian rocks by erosion accompanied Quaternary displacement along the fault. The B–B fault has reverse separation, northeast side up; uplift of the northeast side accompanied displacement, producing higher topography and steeper stream gradients northeast of the fault. No surface expression of the B–B fault has been found northwest of the syntaxis, although the IKSZ and steeper stream gradients continue at least as far as the Indus River, the site of the Pattan earthquake of M 6.2 in 1974. To the southeast, northwest-striking faults were mapped by the Geological Survey of Pakistan. One of these faults, the Riasi thrust, cuts across the southwest flank of an anticline exposing Precambrian limestone. Farther southeast, in Indian-administered territory, Holocene activity on the Riasi thrust has been described. In the Kangra reentrant still farther southeast, active faulting may follow the Soan thrust, along which Holocene and Pleistocene offsets have been described. The Soan thrust, rather than the south flank of the Janauri anticline, may represent the surface projection of the 1905 Kangra earthquake of M 7.8.     

Controls of fluid chemistry and complexation on rare-earth element contents of anhydrite from the Pacmanus subseafloor hydrothermal system,Manus Basin,Papua New Guinea

Ocean Drilling Program (ODP) leg 193 successfully drilled four deep holes (126 to 386 m) into basement underlying the active dacite-hosted Pacmanus hydrothermal field in the eastern Manus Basin. Anhydrite is abundant in the drill core material, filling veins and vesicles, cementing breccias, and occasionally replacing igneous material. We report rare-earth element (REE) contents of anhydrite from a site of diffuse venting (Site 1188) which show extreme variability, in terms of both absolute concentrations (e.g., 0.08–28.3 ppm Nd) and pattern shape (La_N/Sm_N=0.08–3.78, Sm_N/Yb_N=0.48–23.1, Eu/Eu*=0.59–6.1). The range of REE patterns in anhydrite includes enrichments in the middle and heavy REEs and variable Eu anomalies. The patterns differ markedly from those of anhydrite recovered during ODP Leg 158 from the TAG hydrothermal system at the Mid-Atlantic Ridge which display uniform LREE-enriched patterns with positive Eu anomalies, very similar to TAG vent fluid patterns. As the system is active, the host-rock composition is uniform, and the anhydrite veins appear to relate to the same hydrothermal stage, we can rule out predominant host-rock and transport control. Instead, we propose that the variation in REE content reflects waxing and waning input of magmatic volatiles (HF, SO₂) and variable complexation of REEs in the fluids. REE speciation calculations suggest that increased fluoride and possibly sulfate concentrations at Pacmanus may affect REE complexation in fluids, whereas at TAG only chloride and hydroxide complexes play a significant role. The majority of the anhydrites do not show positive Eu anomalies, suggesting that the fluids were more oxidizing than in typical mid-ocean ridge hydrothermal systems. We use other hydrothermal fluids from the Manus Basin (Vienna Woods and Desmos), which bracket the Pacmanus fluids in terms of acidity and ligand concentrations, to examine the dependence of REE complexation on fluid composition. Geochemical modeling reveals that under the prevailing conditions at Pacmanus (pH~3.5, T=250–300 °C), Eu oxidation state and the relative importance of fluoride versus chloride complexing are very sensitive to small variations in oxygen fugacity, temperature, and pH. Patterns with extreme mid-REE enrichment may reflect speciation effects (free-ion abundance) coupled with crystal chemical control. We conclude that the great variability in REE concentrations and pattern shape is likely due to variable fluid composition and REE complexation in the fluids. Editorial handling: L. Meinert