Bacterial influence on storage and mobilisation of metals in iron-rich mine tailings from the Salobo mine, Brazil.

In this study we investigated the potential effects of promoting bacterial activity on tailings from the Salobo iron-oxide copper­gold (IOCG) mine, Brazil. In particular we focussed on (1) the potential for mobilising additional Cu and (2) the effects of long-term storage on other metals. Unlike typical sulphide-ore tailings, the pH of the Salobo tailings is circumneutral and these tailings are dominated by Fe-bearing silicates and magnetite, with minor micrometre-scale encapsulated Cu-bearing sulphides. While these tailings do not produce acid mine drainage, an endemic strain of Acidithiobacillus ferrooxidans was isolated from the mine site. These bacteria were used in laboratory column leaching experiments of tailings material, which ran for up to 395 days, without the addition of ferrous iron. Bacteria-tailings interactions were typically maintained at a pH > 5, due to silicate-mediated pH buffering. This was eventually overcome after ~200 days by regular addition of acidic (pH 2.2) nutrient solution, as well as growth and acid generation by bacteria. Copper dissolution was not significantly enhanced by bacterial activity compared to abiotic control experiments while pH was >5. However, as the experiments were progressively acidified, additional Cu was mobilised in the biotic systems. The mineral alteration reactions produced abundant ferrihydrite precipitates within the tailings, which was enhanced by bacterial activity as the pH decreased. Adsorption of metal cations to these precipitates ensured that effluent solutions had only low levels (<0.5 mg/l) of dissolved trace metals such as As, Co, Pb, Zn, Se, Ni and Cr. These adsorption processes will strongly inhibit metal leaching from the tailings during long-term storage, as long as the iron oxidising bacteria are producing the requisite excess of ferrihydrite and the pH is >5. This case study shows that bacterially-mediated silicate weathering, in Fe(II)-bearing silicate rich tailings with only minor sulphides and Acidithiobacillus ferrooxidans can enhance the environmental stability of the tailings.

Phytostabilization of gold mine tailings, New Zealand. Part 1: Plant establishment in alkaline saline substrate.

Tailings from the Macraes mine, southern New Zealand, are prone to wind erosion. Use of a vegetation cover for physical stabilization is one potential solution to this environmental problem. This study used field trials contained in lysimeters to 1), test the ability of different plant species to grow in un/amended tailings and 2), provide background information on the nutrient and chemical content of waters in tailings. Barley (Hordeum vulgare), blue lupin (Lupinus angustifolius), and rye corn (Secale cereale) were trialed, using Superphosphate fertilizer and sewage sludge as amendments. Rye corn grew well in fertilizer-amended tailings, but poorly in unamended tailings; barley growth was similar in amended and unamended tailings; blue lupins grew poorly overall The tailings had alkaline pH (7-8.5) and water rapidly (< 1 mo) interacted with the tailings to become strongly saline. Minor acid generation was neutralized by calcite, with associated release of calcium and carbonate ions. Leachate waters were supersaturated with respect to calcite and dolomite. Dissolved sodium concentrations were up to 1000 mg L(-1), but elevated Ca2+ calcium and Mg2+ ensured that sodicity was lower than plant-toxic levels. Rye corn is a potentially useful plant for rapid phytostabilization of tailings, with only minor phosphate amendment required.

Phytostabilization of gold mine tailings from New Zealand. Part 2: Experimental evaluation of arsenic mobilization during revegetation.

Revegetation of mine tailings usually requires amendments of phosphorus. However, phosphate addition can mobilize arsenic (As) from the tailings. A 5-mo lysimeter field trial was conducted to quantify As mobilization in gold mine tailings, in association with different P amendment products and different plant species (barley Hordeum vulgare, blue lupin Lupinus angustifolius, rye corn Secale cereale) necessary for short-term revegetation of mine tailings. A simultaneous laboratory experiment was run to examine As mobilization in 1-cm-deep tailings in relation to different P amendment rates. The experimental results showed that the amount of As leached was proportional to the amount of P added. In the larger scale lysimeters, P amendment of < 3 g m(-2) caused As leaching of 0.5 mg L(-1) from unplanted lysimeters and up to 0.9 mg L(-1) on average in planted lysimeters. Variable species-amendment combinations produced differences in the amount of As leached and uptaken. Leachates and uptakes were higher with an organic fertilizer amendment than Superphosphate, particularly in combination with barley. Arsenic accumulated in plant biomass to 126 mg kg(-1) in shoots and 469 mg kg(-1) in roots.

River capture, range expansion, and cladogenesis: the genetic signature of freshwater vicariance.

River capture is potentially a key geomorphological driver of range expansion and cladogenesis in freshwater-limited taxa. While previous studies of freshwater fish, in particular, have indicated strong relationships between historical river connections and phylogeographic pattern, their analyses have been restricted to single taxa and geological hypotheses were typically constructed a posteriori. Here we assess the broader significance of river capture among taxa by testing multiple species for the genetic signature of a recent river capture event in New Zealand. During the Quaternary an upper tributary of the Clarence River system was diverted into the headwaters of the Wairau River catchment. Mitochondrial DNA (control region and cytochrome b) sequencing of two native galaxiid fishes (Galaxias vulgaris and Galaxias divergens) supports headwater exchange: populations from the Clarence and Wairau Rivers are closely related sister-groups, whereas samples from the geographically intermediate Awatere River are genetically divergent. The upland bully Gobiomorphus breviceps (Eleotridae), in contrast, lacks a genetic signature of the capture event. We hypothesize that there is an increased likelihood of observing genetic signatures from river capture events when they facilitate range expansion, as is inferred for the two galaxiid taxa studied here. When river capture merely translocates genetic lineages among established populations, by contrast, we suggest that the genetic signature of capture is less likely to be retained, as might be inferred for G. breviceps. Rates of molecular evolution calibrated against this recent event were elevated relative to traditional estimates, consistent with the contribution of polymorphisms to branch lengths at shallow phylogenetic levels prior to fixation by purifying selection and drift.

Mobilisation and attenuation of boron during coal mine rehabilitation, Wangaloa, New Zealand.

Environmental mobility and fate of boron has been traced from source to discharge waters through the rehabilitated Wangaloa coal mine in southern New Zealand. The boron is derived initially from coal, which has up to 450 mg/kg B. The coal also contains pyrite (2-5 wt.% S), which oxidizes to yield a low-pH environment (typical pH 2-5). Weathering of coal-bearing waste rock liberates B into rainwater that infiltrates into waste rock or evaporates to leave a gypsum crust enriched in B, possibly as boric acid or colemanite as inferred from geochemical modelling. Surface waters dissolve this evaporative material periodically, yielding total B concentrations up to 6 mg/L, at pH<4.5. Some of the available B is taken up by plants that have been established on the waste rock, resulting in foliage B concentrations of up to 230 mg/kg (dry weight). Partial attenuation of dissolved B by adsorption to iron oxyhydroxide occurs as groundwater passes through waste rock, but this is inhibited by adsorption competition with dissolved sulphate (up to 600 mg/L). Groundwater flows from the mine through a pit lake and wetland, with total dissolved B near 1 mg/kg after dilution and limited adsorption attenuation has occurred. Despite the widespread B mobility throughout the rehabilitated mine, there is little evidence of B toxicity in plants. The B concentrations in discharging waters are in the environmentally safe range for most aquatic organisms, being neither deficient in B as a micronutrient, nor boron-toxic.

Potential anthropogenic mobilisation of mercury and arsenic from soils on mineralised rocks, Northland, New Zealand.

Eroded roots of hot spring systems in Northland, New Zealand consist of mineralised rocks containing sulfide minerals. Marcasite and cinnabar are the dominant sulfides with subordinate pyrite. Deep weathering and leached soil formation has occurred in a warm temperate to subtropical climate with up to 3 m/year rainfall. Decomposition of the iron sulfides in natural and anthropogenic rock exposures yields acid rock drainage with pH typically between 2 and 4, and locally down to pH 1. Soils and weathered rocks developed on basement greywacke have negligible acid neutralisation capacity. Natural rainforest soils have pH between 4 and 5 on unmineralised greywacke, and pH is as low as 3.5 in soils on mineralised rocks. Roads with aggregate made from mineralised rocks have pH near 3, and quarries from which the rock was extracted can have pH down to 1. Mineralised rocks are enriched in arsenic and mercury, both of which are environmentally available as solid solution impurities in iron sulfides and phosphate minerals. Base metals (Cu, Pb, Zn) are present at low levels in soils, at or below typical basement rock background. Decomposition of the iron sulfides releases the solid solution arsenic and mercury into the acid rock drainage solutions. Phosphate minerals release their impurities only under strongly acid conditions (pH<1). Arsenic and mercury are adsorbed on to iron oxyhydroxides in soils, concentrated in the C horizon, with up to 4000 ppm arsenic and 100 ppm mercury. Waters emanating from acid rock drainage areas have arsenic and mercury below drinking water limits. Leaching experiments and theoretical predictions indicate that both arsenic and mercury are least mobile in acid soils, at pH of c. 3-4. This optimum pH range for fixation of arsenic and mercury on iron oxyhydroxides in soils is similar to natural pH at the field site of this study. However, neutralisation of acid soils developed on mineralised rocks is likely to decrease adsorption and enhance mobility of arsenic and mercury. Hence, development of farmland by clearing forest and adding agricultural lime may mobilise arsenic and mercury from underlying soils on mineralised rocks. In addition, arsenic and mercury release into runoff water will be enhanced where sediment is washed off mineralised road aggregate (pH 3) on to farm land (pH>6). The naturally acid forest soils, or even lower pH of natural acid rock drainage, are the most desirable environmental conditions to restrict dissolution of arsenic and mercury from soils. This approach is only valid where mineralised soils have low base metal concentrations.

Rapid plant-cover establishment on gold mine tailings in southern New Zealand: glasshouse screening trials.

The use of a short-term vegetation cover to temporarily control the negative environmental effects of inactive tailings ponds is notfrequently practiced during operational mining, but could have some merit This article reports on a glasshouse trial designed to examine some of the issues associated with short-term vegetation: fast germination of a high proportion of seed, the ability of seedlings to survive in unamended substrates, and potentially toxic substrate. Five nonindigenous plant species were tested--barley (Hordeum vulgare), rye corn (Secale cereale), Italian ryegrass (Lolium multifiorum), red clover (Trifolium pratense), and lucerne (Medicago sativa)--in five different types of substrate: unamended tailings, tailings and fertilizer, tailings and greenwaste, biosolid-blend compost, and local topsoil. The nutrient and heavy metal status (As, Cu, Cd, Ni, Pb) of each substrate type was determined Plant species performance was monitored over 14 wk Substrate metal concentrations were low except for As, which was elevated in all substrate types. Plants in unamended tailings grew less vigorously than plants in tailings and compost or in topsoil. Plant performance in tailings and fertiliser was greatly suppressed following a high fertilization rate. Metal uptake in plants was highest for As (0.4-77 mg kg(-1) DW) and Cu (5.3-50.3 mg kg(-1) DW). Future field trials are necessary to authenticate findings, but barley and rye corn are promising species for a short-term tailings cover.

Antimony distribution and environmental mobility at an historic antimony smelter site, New Zealand.

A historic antimony smelter site at Endeavour Inlet, New Zealand has smelter residues with up to 17 wt.% antimony. Residues include coarse tailings (cm scale particles, poorly sorted), sand tailings (well sorted) and smelter slag (blocks up to 30 cm across). All of this material has oxidised to some degree over the ca. 100 years since the site was abandoned. Oxidation has resulted in acidification of the residues down to pH 2-5. Smelter slag contains pyrrhotite (FeS) and metallic antimony, and oxidation is restricted to surfaces only. The coarse tailings are the most oxidised, and few sulfide grains persist. Unoxidised sand tailings contain 10-20 vol.% stibnite (Sb2S3) containing up to 5% As, with subordinate arsenopyrite (FeAsS), and minor pyrite (FeS2). The sand tailings are variably oxidised on a scale of 2-10 cm, but original depositional layering is preserved during oxidation and formation of senarmontite (Sb2O3). Oxidation of sand tailings has resulted in localised mobility of both Sb and As on the cm scale, resulting in redistribution of these metalloids with iron oxyhydroxide around sand grain boundaries. Experiments demonstrate that Sb mobility decreases with time on a scale of days. Attenuation of both As and Sb occurs due to adsorption on to iron oxyhydroxides which are formed during oxidation of the smelter residues. There is no detectable loss of Sb or As from the smelter site into the adjacent river, <50 m away, which has elevated Sb (ca. 20 microg/l) and As (ca. 7 microg/l) from mineralised rocks upstream. Despite the high concentrations of Sb and As in the smelter residues, these metalloids are not being released into the environment.

Mobilisation and bioavailability of arsenic around mesothermal gold deposits in a semiarid environment, Otago, New Zealand.

Arsenopyrite (FeAsS) is the principal arsenic (As) mineral in mineralised mesothermal veins (typically 5,000 mg/kg As) in southeastern New Zealand. Groundwater in contact with arsenopyrite-bearing rocks has elevated As concentrations (up to 0.1 mg/l). The arsenopyrite decomposes slowly on oxidation in soils and historic mine workings in a cool semiarid climate. Dissolved As is predominantly As(III) in association with arsenopyrite, but this is rapidly oxidised over days to weeks to As(V) in the vadose zone. Oxidation is facilitated by particulate Fe and/or Mn oxyhydroxides, and by bacteria in surface waters. Evaporative concentration of dissolved As(V) in the vadose zone causes precipitation of scorodite (Fe(III)As(V)O4*2H2O). Adsorption of As(V) to Fe oxyhydroxides in soils and groundwater pathways lowers dissolved As concentrations. Soils over mineralised veins typically have <200 mg/kg As, as most As is removed in solution on geological time scales. Most plants on the mineralised rocks and soils do not take up As, although some inedible species can fix up to 18 mg/kg As. Hence, bioavailability of As(V) is low in this environment, despite the substantial As flux. Similar As mobility is seen in an active gold mine processing plant and tailings. Arsenopyrite dissolves more rapidly on agitation, and mine waters can have dissolved As >200 mg/l, predominantly as As(V). This dissolved As decreases in tailings waters to near 2 mg/l, mainly as As(III) when in contact with arsenopyrite. Weak oxidation of evaporatively dried tailings causes cementation with scorodite and iron oxyhydroxides, and scorodite precipitation exerts some control on dissolved As(V) concentrations. High dissolved As in mine waters is lowered by adsorption to iron oxyhydroxides, and waters discharged from the mine site have negligible dissolved As.

Genes meet geology: fish phylogeographic pattern reflects ancient, rather than modern, drainage connections.

We used DNA analysis of the freshwater Galaxias vulgaris complex (Pisces: Galaxiidae) to test a geological hypothesis of drainage evolution in South Island, New Zealand. Geological evidence suggests that the presently north-flowing Nevis River branch of the Clutha/Kawarau River system (Otago) once flowed south into the Nokomai branch of the Mataura system (Southland). The flow reversal is thought to have resulted from fault and fold activity associated with post-Miocene uplift. Mitochondrial DNA sequence data (control region and cytochrome b genes; 76 individuals; maximum divergence 7.1%) corroborate this geomorphological hypothesis: The Nevis River retains a freshwater fish species (Galaxias gollumoides; five sites; 10 haplotypes) that is otherwise restricted to Southland (nine sites; 15 haplotypes). There is no indication that the Nevis River lineage of G. gollumoides lives elsewhere in the Clutha/ Kawarau system (> 30 sites). Likewise, two widespread Clutha lineages (G. 'sp D'; G. anomalus-G. pullus) are apparently absent from the Nevis (> 30 sites). In particular, G. 'sp D' lives throughout much of the Clutha (12 sites, 23 haplotypes), including a tributary of the Kawarau, but is absent from the Nevis itself. Conventional molecular clock calibrations (based on a minimum Nevis-Mataura haplotype divergence of 3.0%) indicate that the Nevis flow reversal may have occurred in the early-mid Pleistocene, which is roughly consistent with geological data. The broad phylogeographic structure evident in the Clutha system is consistent with the sedentary nature of nonmigratory galaxiids. Our study reinforces the value of combining biological and geological data for the formulation and testing of historical hypotheses.