Consolidation and incipient oxidation of alkaline arsenopyrite-bearing mine tailings,Macraes Mine,New Zealand

Fine grained (ca. 15 μm), arsenopyrite-bearing mine tailings have been exposed to drying and oxidation for 4 a pending relocation. The tailings are still partly covered by a pond of decanted pore waters. The water table in drying tailings has lowered by 1–3 m and desiccation cracks up to 2 cm wide have formed on the 1 m scale, extending through the unsaturated zone. Tailings in the unsaturated zone have similar pore water contents to saturated tailings: typically 16–32 wt% water. Saturated tailings retain alkaline pH (ca. 10) from the mine cyanidation plant, but pH lowers progressively towards ca. 7 near the surface, or near desiccation cracks, in the unsaturated zone. The redox state of the tailings changes in parallel with pH, with an empirical relationship: Eh(mV)=−55 pH+290. Water in the remnant decant pond reflects this relationship also. Unsaturated tailings have variable but low permeabilities, typically 10⁻³ to 10⁻⁴ m/day, and more permeable horizons have allowed incursion of oxygenated air and/or rain water from desiccation cracks. Sulphide grains in all tailings examined are unaltered. Sulphides and solutions in the tailings are out of thermodynamic equilibrium predicted from the redox–pH conditions, due to kinetic constraints. Incursion of rain water locally facilitates deposition from pore waters of insoluble Fe oxide and arsenate minerals, thus fixing As in the dry unsaturated tailings.     

Geological controls on refractory ore in an orogenic gold deposit, Macraes mine, New Zealand

The Macraes mine is hosted in an orogenic (mesothermal) gold deposit in metasedimentary rocks of the Otago Schist belt. Much gold occurs within altered schist with minimal silica-addition, and this study focuses on altered schist ore types. The unmineralized host schists are chemically and mineralogically uniform in composition, but include two end-member rock types: feldspathic schist and micaceous schist. Both rock types have undergone hydrothermal alteration along a shallow-dipping foliation-parallel shear zone, but their different rheological properties have affected the style of mineralisation. Micaceous schist has been extensively recrystallized and hydrothermally altered during ductile deformation, to form ores characterized by abundant, disseminated millimetre-scale pyrite cubes (typically 1–2 wt% S) and minor silicification. The earliest pyrite contained Ni and/or As in solid solution and no gold was imaged in these pyrites or later arsenopyrite grains. The ore type is refractory and gold recovery by cyanide leaching is less than 50%, with lowest recovery in rocks that have been less affected by later brittle deformation. In contrast, hydrothermally altered feldspathic schist is characterized by mineralised black microshears and veinlets formed during shear-zone related brittle deformation. Microsheared ore has relatively low sulphur content (<0.7 wt%) and muscovite has been illitised during hydrothermal alteration. Pyrite and arsenopyrite in microshears are fractured and deformed, and contain 1–10 m blebs of gold. Later pyrite veinlets also contain micron- to submicron-scale inclusions of sphalerite, chalcopyrite, galena, and gold (10 microns). Gold in microsheared ore is more readily recoverable than in the refractory ore, although encapsulation of the fine gold grains inhibits cyanidation. Both microsheared ore and disseminated pyritic ore pass laterally into mineralised black shears, which contain hydrothermal graphite and late-stage cataclastic sulphides. This black, sheared ore releases gold readily, but the gold is then adsorbed on to gangue minerals (preg-robbed) and net cyanidation recovery can be less than 50%. Hence, low gold recovery during cyanidation results from (1) poor liberation of gold encapsulated in microcrystalline quartz and unfractured sulphide grains, and (2) preg-robbing of liberated gold during cyanidation. Introduction of pressure-oxidation of ore prior to cynidation has mitigated these issues.     

Arsenic distribution during formation and capping of an oxidised sulphidic minesoil, Macraes mine, New Zealand

A minesoil has developed over 5 years oxidative exposure on sulphide concentrate tailings (ca. 1 wt.% As) at the Macraes mesothermal gold mine, New Zealand. The minesoil has a dry crust which has formed due to evaporative drying. This dry crust is enriched in arsenic (ca. 5 wt.% As) as scorodite (FeAsO₄·2H₂O) because of upward mobility of dissolved arsenic during drying. Similar enrichment of arsenic has occurred along the walls of desiccation cracks which extend over 1 m into the minesoil. Capping of the tailings and minesoil with wet tailings (pH=8) results in dissolution of scorodite and remobilization of arsenic on the millimetre scale. Experimental capping of the minesoil with wet calcium carbonate remobilized some arsenic from scorodite on the centimetre scale, but much original arsenic enrichment was preserved after 400 days. A layer of gypsum (CaSO₄·2H₂O) and iron oxyhydroxide cementation developed at the interface between the minesoil and the experimental calcium carbonate cap, restricting water flow. This layer was ca. 1 mm thick after 400 days. Theoretical comparison between advection and diffusion in the minesoil suggests that diffusion is an important mechanism for chemical mobility on the 1–50-year time scale. However, advection can be important in secondary porosity of the dry crust of the minesoil and water penetrates this zone at a rate of 1.5 mm/day.     

Kilometre-scale structural setting of ore shoots in the Frasers gold deposit,Macraes mine,New Zealand

The Hyde-Macraes Shear Zone in southern New Zealand contains the circa 10 million ounce Macraes gold deposit, one of the larger Phanerozoic orogenic gold deposits discovered to date globally. Approximately 50% of this 10 million ounce resource is hosted by 5 major ore shoots up to 400 m wide and 1500 m long in the Frasers area at the southern end of the mine. Higher grade (>1.5 g/t Au) ore shoots are located along and immediately below the Hangingwall Shear, the principal strand of the Hyde-Macraes Shear Zone at the Frasers deposit. They typically trend parallel to the intersection of the shear and foliation in the underlying schist, commonly where the foliation dips more steeply that the overlying Hangingwall Shear. Especially thick zones of higher grade mineralised rock are located between the Hangingwall Shear and underlying second order splay shears whose position correlates with minor right-hand bends in the strike of the overlying Hangingwall Shear. Lower grade (<1.2 g/t Au), but economically significant, ore shoots are located within mineralised schists below the Hangingwall Shear. Outer margins of these lower grade ore shoots are generally parallel to the strike of the foliation in the host schist. They are most extensive where open disharmonic folding has resulted in the strike of the foliation diverging from that of the overlying Hangingwall Shear. No correlation exists between the position of any ore shoots and gently dipping jogs in the Hangingwall Shear, despite mineralisation occurring during reverse movement on the Hyde-Macraes Shear Zone. Instead the angular relationship between various strands of the Hyde-Macraes Shear Zone at Frasers and foliation in underlying schists is the most consistent structural feature likely to predict the location, extent, and orientation of ore shoots within the Frasers segment of the Hyde-Macraes Shear Zone.     

Contrasting coeval paragenesis of gold and scheelite in an orogenic hydrothermal system,Macraes mine,New Zealand

The Macraes deposit (> 10 Moz resource) is a Cretaceous orogenic system hosted in the Hyde-Macraes Shear Zone (HMSZ) which was mineralised under lower greenschist facies during later stages of lower greenschist facies metamorphism of host metasedimentary schists. Gold is encapsulated primarily in sulphides that have replaced silicates in ductile shears that are focussed in micaceous rocks. The shears anastomose around structurally competent lenses, and were enhanced by hydrothermal graphite deposition and alteration of albite to muscovite. In contrast, scheelite with minor auriferous sulphides occurs in multigenerational quartz veins that filled fractures in competent lithologies. Hence, scheelite was deposited coevally with gold, from the same hydrothermal fluid, but in different structural settings from most gold at all scales from millimetres to hundreds of metres. Consequentially, there is weak correlation between Au and W at all scales in the deposit. Multigenerational gold and scheelite mineralisation occurred during progressive deformation in the shear zone in two contrasting structural and mineralogical styles in syn-deformationally weakening gold-bearing micaceous shears, and in syn-deformationally hardened competent rocks that became silicified and veined with quartz and scheelite. Hydrothermal fluid flow in the gold-bearing shears occurred at the grain boundary, microshear, and microfracture scales, and was slow (< 1 m/year), continuous, and pervasive. In contrast, vein formation in more competent lithologies was episodic, locally rapid (> hundreds of m/year), and was controlled by fracture permeability. The Au and W enrichment in the Macraes deposit resulted from regional scale metal mobility, driven by coeval recrystallisation in higher-grade (upper greenschist to amphibolite facies) metamorphism that persisted structurally below the Macraes deposit for at least 10 Ma after mineralisation ceased.     

Geological analogue for circumneutral pH mine tailings: implications for long-term storage,Macraes Mine,Otago, New Zealand

Tailings from the Macraes Au mine cyanidation process are stored in an impoundment about 0.6 km² and 80 m deep whose pH is maintained near 8 by the neutralizing capacity of the gangue minerals. The tailings are sandy (>50 μm particles), have a hydraulic conductivity of about 10⁻² m/day, and contain 0.1–1.0 wt.% S and 0.1–1.5 wt.% graphitic C from the primary deposit. Concentrations of As in the pore water of the mixed tailings, which are a combination of various tailings types, range from 0.1 to 20 ppm, HCO₃^- is 100 to 200 ppm, and dissolved SO₄ is 100–1700 ppm. The mixed tailings will be stored in this impoundment in perpetuity after mining ceases. Confidence in the long-term pH stability of these tailings can be gained from examination of mineralogically and chemically similar geological analogues in the immediate vicinity. A sequence, typically about 5 m thick, of sands and gravels derived from the Macraes mineralized zone 12–28 ka ago contains rounded detrital sulfide mineral grains which are unoxidized despite their close proximity to the surface and the occasional incursion of oxygenated waters. These sediments have a hydraulic conductivity of about 10⁻⁴ m/day. Saturating water pH is currently 7–8. Sands with 0.2–0.8 wt.% organic C host SO₄-reducing bacteria (SRB), and local cementation by authigenic framboidal pyrite has occurred. SRB were found in water-saturated sediments with decreased hydraulic conductivity and alkaline and anoxic conditions. These bacteria are involved in the formation of authigenic framboidal pyrite, reducing the cycling of dissolved Fe in the sediments. Carbon is not a limiting factor in this process as organic matter is present in the sandstone and ground water contains up to 180 ppm HCO₃^-. Comparison of the 28 ka old sediments with the modern tailings suggests that the chemical behaviour of the two will be similar, possibly with the crystallization of authigenic pyrite in the tailings over the long term. As long as the present slightly anoxic and circumneutral pH environmental conditions are maintained in the mixed tailings impoundment, sulfide decomposition and acidification are unlikely.     

Geochemistry of late metamorphic hydrothermal alteration and graphitisation of host rock, Macraes gold mine, Otago Schist, New Zealand

The Macraes gold deposit in the Otago Schist, New Zealand, formed during late metamorphic fluid flow through a lower greenschist facies shear zone. Mineralisation occurred near to the brittle-ductile transition at about 300 °C. Large volumes of host rock in a shear zone up to 120 m thick have been hydrothermally altered by this fluid activity. Most alteration is not structurally controlled apart from proximity to the shear zone. Ductile and brittle microshears traverse the most mineralised rocks and some structural control of fluid flow occurred as well. Fluid flow was slow, similar to that in metamorphic rocks (mm/year) and diffusion through interconnected fluid was a significant chemical process. Localised extensional hydrofractures (m scale) are filled with mineralised quartz. Most alteration of the host rocks was isochemical with respect to the lithophile elements, and mineralised rocks have been variably enriched in As, Au, Sb, W, Mo and Bi, but not Co or Cd. Addition of sulphur has occurred to both host rocks and mineralised rocks, up to 1 wt.% above a background of 0.1 wt.%. Host rock sulphur is mainly pyritic and is not structurally controlled. Mineralised rocks have pyrite and arsenopyrite along microshears. Pyrite, chalcopyrite, sphalerite and galena have formed from sulphidation of silicates with no addition of metals. Graphite has been added to mineralised rocks along microshears, up to 3 wt.% locally, above a background of 0.1 wt.% noncarbonate carbon. Graphite deposition may have occurred as a result of mixing of two fluids, water+methane, and water+carbon dioxide. Graphitisation and sulphidation reactions released low δD water, which accumulated in the slow-moving mineralising fluid. Distinction between this low δD reaction water and meteoric water incursion is difficult.     

Contributions of discharges from a historic antimony mine to metalloid content of river waters,Marlborough, New Zealand

Historic antimony mining at Endeavour Inlet, New Zealand, was developed in a stibnite-rich mesothermal vein system hosted in a km scale shear zone in metasedimentary schist. The schist contains calcite, and all waters have pH between 7 and 8. Underground tunnels (adits) have largely collapsed, but two adits provided access to waters which have interacted chemically with mineralised rock. Natural groundwater entering an adit at the top of the mineralised catchment had 190 μg/l Sb and 10 μg/l As. The amount of arsenic increased along the adit as the water interacted with arsenopyrite-bearing rocks and debris (up to 2000 mg/kg As, 500 mg/kg Sb) on the adit floor. Sb(III) was below 14 μg/l, and there was no detectable As(III). Antimony content remained near constant in the adit but increased outside the adit because of interaction with stibnite-rich debris. Negligible attenuation of metalloids occurred via adsorption outside the adit, as iron oxyhydroxide is rare. Metalloid attenuation was by dilution in a nearby natural stream, which carried <30 μg/s Sb and <10 μg/s As away from the site. An adit 500 m downstream was developed in a lower, more arsenopyrite-rich portion of the mineralised system with debris containing up to 15,000 mg/kg As and 5000 mg/kg Sb. Water from this adit had up to 200 μg/l Sb and 1650 μg/l As. Arsenic was attenuated by adsorption outside this adit, and by dilution by the natural stream. Antimony was not attenuated by adsorption, nor by dilution as the natural stream contained up to 200 μg/l Sb. Metalloid flux away from this site was ca. 200 μg/s Sb and 40 μg/s As, and the adit contributed negligible amounts of metalloids to this flux. Total metalloid flux from the catchment is 14,000 μg/s antimony and 5000 μg/s arsenic, which is around three orders of magnitude greater than observed mine inputs to the catchment. Highest flux occurred in September as water tables rose in the winter. Nearly all the metalloid flux is derived by natural groundwater and surface water interaction with mineralised rock. This interaction between water and mineralised rock is enhanced in this area because the catchment runs subparallel to the shear zone which controls the mineralised veins.     

Environmental characterisation of coal mine waste rock in the field: an example from New Zealand

Characterisation of mine waste rock with respect to acid generation potential is a necessary part of routine mine operations, so that environmentally benign waste rock stacks can be constructed for permanent storage. Standard static characterisation techniques, such as acid neutralisation capacity (ANC), maximum potential acidity, and associated acid–base accounting, require laboratory tests that can be difficult to obtain rapidly at remote mine sites. We show that a combination of paste pH and a simple portable carbonate dissolution test, both techniques that can be done in the field in a 15 min time-frame, is useful for distinguishing rocks that are potentially acid-forming from those that are acid-neutralising. Use of these techniques could allow characterisation of mine wastes at the metre scale during mine excavation operations. Our application of these techniques to pyrite-bearing (total S = 1–4 wt%) but variably calcareous coal mine overburden shows that there is a strong correlation between the portable carbonate dissolution technique and laboratory-determined ANC measurements (range of 0–10 wt% calcite equivalent). Paste pH measurements on the same rocks are bimodal, with high-sulphur, low-calcite rocks yielding pH near 3 after 10 min, whereas high-ANC rocks yield paste pH of 7–8. In our coal mine example, the field tests were most effective when used in conjunction with stratigraphy. However, the same field tests have potential for routine use in any mine in which distinction of acid-generating rocks from acid-neutralising rocks is required. Calibration of field-based acid–base accounting characteristics of the rocks with laboratory-based static and/or kinetic tests is still necessary.     

Numerical modelling of mechanical controls on coeval steep and shallow dipping auriferous quartz vein formation in a thrust zone,Macraes mine,New Zealand

The Hyde-Macraes Shear Zone (HMSZ) is a regionally continuous, low-angle, NE dipping (~15°) late-metamorphic thrust zone in the Mesozoic Otago Schist. The shear zone, which is host to large volumes of mineralised schist, consists of foliated fissile schist with some massive schist pods. Two sets of quartz veins are found within the HMSZ: thrust-related, shallowly dipping veins that were emplaced parallel or sub-parallel to the shears and swarms of steeply dipping extensional veins, which cut across the metamorphic foliation. The latter are restricted to the massive schist pods. Mutual cross-cutting relationships occur between steep extensional veins and shallow-dipping veins, suggesting that they formed contemporaneously. The co-existence of these two vein types locally implies local rotation of the principal stress axes to produce extensional veins within a regional thrust setting. The steep extensional veins are spatially related to lateral and oblique ramps within the HMSZ. Three-dimensional mechanical models show that these lateral or oblique ramps can produce favourable conditions for extensional vein formation when combined with a high fluid pressure and oblique convergence. Mechanical requirements include a reduced differential stress, a positive volumetric strain and an increase in the horizontal shear stress. Our models show that under certain conditions, it is possible for extension-related structures to form during shortening because of local changes in the stress state without the need for a regional scale switch in the imposed stress field. The convergence direction across the HMSZ during formation of the steep extensional veins was ~WNW.     

Origin and deposition of a graphitic schist-hosted metamorphogenic Au-W deposit,Macraes, East Otago,New Zealand

The Macraes gold-tungsten deposit occurs in a low-angle thrust system in biotite grade Otago Schist. Native gold, scheelite, pyrite and arsenopyrite are found in and adjacent to quartz veins and silicified schist of lenticular reef zones, where the thrust system cuts through graphitic pelitic schist. Mineralization is confined to a shear zone, up to 80 m thick, which is closely sub-parallel to the regional schistosity. Chemical alteration is dominated by silicification, with some addition of Cr and depletion of Sr and Ba. Alteration extends only about 5 m from major veins. Oxygen becomes isotopically heavier away from veins due to temperature decrease as hot fluids penetrated into cooler (250°C?) rock. Graphite within the shear zone rocks has reflectance of 6–7% (in oil), similar to graphite in medium-high grade Otago Schist, and is presumed to be metamorphic in origin. This graphite has acted as a reducing agent to cause precipitation of gold where the thrust system, acting as a conduit for metamorphic fluids, intersects the graphitic schist. The metals were derived from the underlying schist pile which may include an over-thrust oceanic assemblage containing metal-enriched horizons.     

Raman characterization of carbonaceous material in the Macraes orogenic gold deposit and metasedimentary host rocks,New Zealand

Raman spectroscopic and petrographic analyses were performed on samples collected from zones distal and proximal to the Macraes gold deposit in the Otago Schist of New Zealand to characterize the features and possible origins of Carbonaceous Material (CM) and to assess the potential role of CM in the formation of gold deposits. CM is a common component in meta-sedimentary orogenic gold deposits, and it has been proposed that CM contributes to gold mineralization processes, but the details of the mechanisms responsible are not fully understood. Documentation of the origins of the Otago schist CM will improve our understanding of the role of CM in gold deposits.This work has identified four types of CM of varying thermal maturity and origins from prehnite–pumpellyite grade to lower greenschist grade samples. In prehnite–pumpellyite and pumpellyite–actinolite grade rocks, low-maturity CM 1 coexists with framboidal pyrite, indicating an in-situ, sedimentary origin, with a potential association with the source of gold. Low crystallinity CM 2 is also found in low grade samples and is likely to have been deposited from fluids unrelated to gold mobilization. CM 3 is the highest maturity CM recognized. CM 3 is found in samples from the highest metamorphic grades studied (lower greenschist facies), where bands of CM 3 cross cut the foliation, CM 3 is therefore thought to have been transported by fluids, though possibly only at short length scales. CM 4 is less mature than CM 3 and is found in mineralized rocks in association with sulfide minerals and gold. CM 4 is likely to have a depositional origin but its precise role with respect to gold mineralization has not been identified.     

(Ruby--Sapphire)--Chromian Mica--Tourmaline Rocks from Westland, New Zealand

Boulders of the assemblage ruby—sapphire corundum, chromianmuscovite, margarite, tourmaline (chromian chlorite, Zn—Mnchromite and Mn—Ti magnetite) occur in glacial moraineand rivers of north Westland, South Island of New Zealand. Thelocation, Cr-rich composition of the boulders and the presenceof rare serpentinite rinds indicate that they are derived fromultramafic rocks (Pounamu Ultramafics) that occur within AlpineSchist of the Southern Alps. The largest sample is progressivelyzoned outwards from a corundum—margarite core, throughan intermediate zone of Cr-muscovite, to an outer zone of Cr-chloritethat is in contact with serpentinite. Most finds consist oferosion-resistant corundum-rich cores. In the corundum, Cr₂O₃content ranges from 0.5 to 13%, with red coloration becomingmore intense with increasing Cr. In addition to the dominantCr³⁺ Al³⁺ substitution, those of (Fe, V)³⁺ Cr³⁺ and (Ti⁴⁺+Fe²⁺) 2Cr³⁺ result in spectacular colour zoning from colourlessto deep ruby red-carmine and pale blue to dark blue—violet.Corundum has grown by replacement of the micaceous matrix thatconsists of chromian muscovite (0.10–4.10% Cr₂O₃) andchromian margarite (0.46–1.20% Cr₂O₃). Both micas containa significant paragonite component (up to 21.5% in muscoviteand up to 40.8% in margarite). Late phase muscovite is Ba richwith up to 4.77% BaO, and margarite has up to 0.66% SrO. Tourmalineoccurs as veins, vein outgrowths and larger poikilitic crystalsthat replace the mica matrix. Chromium content ranges between0.82 and 3.6% Cr₂O₃. High bulk rock Al (up to 78% Al₂O₃), K,Ca, Cr and Na, and low Si (14.5–23.1% SiO₂), suggest thatthe corundum—Cr-silicate rocks are the products of extrememetasomatic alteration of quartzofeldspathic schist enclavesin serpentinite. Isocon analysis indicates that conversion ofthe schist to the micaceous matrix of the corundum rocks involvesconservation of Ca, Al, K, volatiles and Sr, a mass loss of59% and a volume reduction of 69% consequent on removal of 70–80%Si and all other elements (most >80%), with enrichment ofbetween 900 and 1800% Cr. The formation of corundum from themica matrix involved a further mass—volume reduction anddecrements in Si, Ca, K, volatiles and Sr from reaction sites.Concentric mineral zonation in single rock samples and zoning—replacementin minerals, e.g. Cr in corundum and chromite, Ti, Fe²⁺ in corundum,Ba in muscovite, Sr in margarite, and Mn and Zn in chromiteand magnetite, imply element redistribution during metasomatism.Experimental reaction between quartzofeldspathic schist andserpentinite at 450C and 2 kbar produced reaction sequencescontaining newly formed Ca-plagioclase—phlogopitic micachloriteand muscovite—chlorite that in terms of composition areanalogous with the observed (corundum—margarite)—muscovite—chloritezonation. The temperature of metamorphism of garnet zone rocks(45020C) that contain the corundum—Cr-silicate rocksis well below that of the breakdown of muscovite and margariteto form corundum and indicates the importance of fluid composition,particularly the cation—hydrogen variables a_Ca²⁺/H⁺, aK⁺/H₊and a_S1O2. Introduction of boron into the schist (from serpentinite),and boron released from the breakdown of original tourmalinein the schist, resulted in tourmaline veining and reaction ofthe mica matrix to form tourmaline that invoved both a massand volume increase and addition of Fe, Mg together with B. KEY WORDS: corundum—Cr-silicate rocks; metasomatism; New Zealand; Southern Alps ^*Corresponding author.     

A predictive model (ETLM) for arsenate adsorption and surface speciation on oxides consistent with spectroscopic and theoretical molecular evidence

The nature of adsorbed arsenate species for a wide range of minerals and environmental conditions is fundamental to prediction of the migration and long-term fate of arsenate in natural environments. Spectroscopic experiments and theoretical calculations have demonstrated the potential importance of a variety of arsenate surface species on several iron and aluminum oxides. However, integration of the results of these studies with surface complexation models and extrapolation over wide ranges of conditions and for many oxides remains a challenge. In the present study, in situ X-ray and infrared spectroscopic and theoretical molecular evidence of arsenate (and the analogous phosphate) surface speciation are integrated with an extended triple layer model (ETLM) of surface complexation, which takes into account the electrostatic work associated with the ions and the water dipoles involved in inner-sphere surface complexation by the ligand exchange mechanism.Three reactions forming inner-sphere arsenate surface species

     

Trace metal adsorption onto urban stream suspended particulate matter (Auckland region,New Zealand)

Trace metal adsorption to suspended particulate matter (SPM) influences bioavailability and toxicity of trace metals in natural waters. For highly contaminated urban catchments in the greater Auckland (New Zealand) area, trace metal adsorption to SPM was assessed and compared to similar data from non-urban catchments in the Auckland region, to determine whether there was any difference in the ability of the SPM to adsorb Cu, Pb and Zn. The degree of trace metal adsorption onto the SPM was assessed by way of adsorption edge experiments. It was found that the ability of the Auckland urban SPM to adsorb trace metals decreased in the order Pb > Cu > Zn. Little difference in adsorption was observed between the non-urban Waikato and Kaipara River SPM and urban SPM, or between urban SPM from different flow regimes and seasons, despite some compositional differences in the SPM. This suggests that on the basis of a single surface-binding site, metal adsorption onto SPM could be readily predicted across a range of urban and non-urban catchments in the Auckland region. Adsorption edges were modelled with a diffuse layer, surface complexation model to assess the role of Fe-oxide in adsorption. The MINTEQA2 model was used, assuming Fe-oxide (as HFO) was the only adsorbing surface. There was generally good agreement between observed and modelled adsorption for Pb, indicating the importance of Fe-oxide surfaces for Pb adsorption. However, the model did not predict Zn or Cu adsorption as well. The TOC content of the SPM, and presence of dissolved ligands and organic matter in the water column, appeared to play an important role in Cu adsorption to the SPM. For Zn, the presence of adsorbing surfaces other than HFO appeared to influence adsorption.     

Thiosulphate in surficial geothermal waters, North Island, New Zealand

Thiosulphate is present in hot springs, streams and thermal pools of the Taupo Volcanic Zone and Ngawha, New Zealand, at concentrations of 1.2 (±1.3) × 10⁻⁵ M to 7.05 (±0.12) × 10⁻⁴M. Formed as a metastable product of sulphide oxidation, thiosulphate is buffered in the presence of elemental S according to, . Unless all sulphide present has been bacterially oxidised to sulphate, a steady state concentration of thiosulphate is maintained. As a soft base thiosulphate is capable of complexing several transition metals. The thermodynamically predicted speciation of Ag in Champagne Pool, for example, indicates a Ag(S₂O₃)₂⁻³ activity similar to that of AgCl₂⁻ though less than that of Ag(HS)₂⁻.     

Accumulation of arsenic from acidic mine waters by ferruginous bacterial accretions (stromatolites)

In the acidic stream (pH 2.2–4) of the Carnoulès Pb-(Zn) mine, Gard, France, very high As contents (from 9 to 20%) can be accumulated as ferric arsenate and arsenate-sulphate precipitates in rapidly growing bacteria-made structures. The main bacterial forms are rod-shaped and sheathed, their sheath is made of Fe-As-rich material and is coated with ferric arsenate colloidal particles or may be partially included in authigenic crystals. Living forms ofThiobacillus-type bacteria have been recognized in the precipitates. The cyclic development of bacterial colonies alternating with sand deposition and erosive episodes results in the formation of As-rich ferruginous accretions. These laminated and dome-shaped bacterial constructions are similar to those of stromatolites. The extremely high contents of solute As in upstream flow (250 mg/1) are lowered by 2–3 order of magnitude downstream. Lead is also precipitated and concentrated in this FeAs-rich bacterial stromatolite (2500 ppm Pb). This accumulation and concentration of As and heavy metals via direct or induced microbial action limits pollution downflow. But seasonal storms could erode these FeAsPb-rich deposits and drastically increase pollution.The accumulation of ferric arsenate by bacterial stromatolites suggests that possible microbial remediation strategies may be used in acid mine drainage environments.     

Mineralogical controls on environmental mobility of arsenic from historic mine processing residues,New Zealand

Processing of arsenopyrite ore took place at Blackwater Au mine, New Zealand, between 1908 and 1951 and no rehabilitation was undertaken after mine closure. High As concentrations in solid processing residues (up to 40 wt% As) are due to secondary As minerals. Site pH regimes vary from 4.1 to circum-neutral. Originally, all processed As was present as arsenolite (arsenic trioxide polymorph, As^III), a by-product of arsenopyrite roasting. Near the roaster, scorodite precipitated as a result of the high dissolved As concentration during arsenolite dissolution. The formation of scorodite has two major consequences. Firstly, the scorodite precipitate cements the ground in the vicinity of the roaster area, thereby creating an impermeable surface crust (up to 30 wt% As) and encapsulating weathered arsenolite grains within the cement. Secondly, formation of scorodite temporarily immobilizes some of the dissolved As that is generated during nearby arsenolite dissolution. Where all the available arsenolite has dissolved, scorodite becomes soluble, and the dissolved As concentrations are controlled by scorodite solubility, which is at least two orders of magnitudes lower than arsenolite solubility. Downstream Eh conditions fall below the As^V/As^III boundary, so that scorodite does not precipitate and dissolved As concentrations are controlled by arsenolite solubility. Dissolved As reaches up to 52 mg/L in places, and exceeds the current WHO drinking water guideline of 0.01 mg/L by 5200 times. This study shows that dissolved As concentrations in discharge waters at historic mine sites are dependent on the processing technology and associated mineralogy.     

Geotechnical characterisation of stratocone crater wall sequences, White Island Volcano, New Zealand

Geotechnical characterisation is undertaken for 3 broad units comprising the bulk of the stratigraphy identified on White Island Volcano, Bay of Plenty, New Zealand, an active island stratovolcano. Field and laboratory measurements were used to describe rock mass characteristics for jointed lava flow units, and ring shear tests were undertaken to derive residual strength parameters for joint infilling materials within the lavas. Rock Mass Rating (RMR) and Geological Strength Index (GSI) values were calculated and converted to Mohr-Coulomb strength parameters using the Hoek-Brown criterion. Backanalysis of known landslide scarps was used to derive strength parameters for brecciated rock masses and hydrothermally altered rock masses. Andesite lava flows have high intact strength (σ_ci = 184 ± 50 MN m^− 2; γ = 24.7 ± 0.3 kN m^− 3) and typically 3 wide, infilled joint sets, one parallel to flow direction and two steeply inclined, with spacings of 0.3-1.7 m. Joints are rough, with estimated friction angles for clean joints of ?_j = 42-47°. Joint infill materials are clayey silts derived from weathering of wall rocks and primary volcanic sources; they have low plastic (54%) and liquid (84%) limits and residual strength values of c_r = 0 kN m^− 2 and ?_r = 23.9 ± 3.1°. RMR values range from 70 to 73, giving calculated strength parameters of c′ = 1161-3391 kN m^− 2 and ?′ = 50.5-62.3°. Backanalysis suggests brecciated rock masses have c′ = 0 kN m^− 2 and ?′ = 35.4°, whereas GSI observations in the field suggest higher cohesion (c′ = 306-719 kN m^− 2) and a range of friction angles bracketing the backanalysed result (?′ = 30.6-41.7°). Hydrothermally altered rock masses have c′ = 369 kN m^− 2 and ?′ = 14.9°, indicating considerable loss of strength, especially frictional resistance, compared with the fresh lava units. Values measured at outcrop scale in this study are in keeping with other published values for similar volcanic edifices; backanalysed data suggest weaker rock mass properties than those determined at outcrop. This is interpreted as a scale issue, whereby rock mass characteristics of a large rock mass (crater wall scale) are weaker than those of small outcrops, due in part to the overestimation of friction angle from measurements on small exposures.