Cook, N. J. 2012. Review: Minimally invasive sampling media and the measurement of corticosteroids as biomarkers of stress in animals. Can. J. Anim. Sci. 92: 227–259. The measurement of ...corticosteroid hormones is commonly used as a biomarker of an animal's response to stress. The difficulties in obtaining blood samples and the recognition of the stressor effect of blood sampling are primary drivers for the use of minimally invasive sample media. In mammals these include saliva, feces, urine, hair, and milk. In birds, samples include excreta, feathers, egg yolk and albumin. In fish, corticosteroids have been measured in excreta and swim-water. Each of these sample media incorporate corticosteroids in accordance with the processes by which they are formed, and this in turn dictates the periods of adrenocortical activity that each sample type represents. Cortisol in saliva represents a time-frame of minutes, whereas the production of feces may be hours to days depending on the species. The longest time-integrations are for hair and feathers which could be over a period of many weeks. The sample media also determines the structural changes that may occur via processes of conjugation to glucuronides and sulfides, metabolic conversion via enzymatic action, and bacterial breakdown. Structural changes determine the optimum methodologies used to measure corticosteroid hormones. In most sample media, measurement of a specific corticosteroid is a requirement depending on the species, e.g., cortisol in most mammals, or corticosterone in birds. However, in samples involving products of excretion, methodologies that measure a broad range of structurally related compounds are probably optimal. The utility of minimally invasive sample media as biomarkers of stress responses depends on the degree to which the corticosteroid content of the sample represents adrenocortical activity. Commonly, this involves comparisons between corticosteroid concentrations in blood plasma with concentrations in the alternative sample media. This review focuses on the methodological and biological validation of corticosteroid measurements in minimally invasive samples as biomarkers of adrenocortical responses to stress.
There is an abundance of published trace element data for sphalerite, galena and chalcopyrite in natural systems, yet for a co-crystallized assemblage comprising these base metal sulphides, there is ...no detailed understanding of the preferred host of many trace elements. Laser-ablation inductively-coupled plasma mass spectrometry trace element maps and spot analyses were generated on 17 assemblages containing co-crystallized sphalerite and/or galena and/or chalcopyrite from 9 different ore deposits. These deposits are representative of different ore types, geologic environments and physiochemical conditions of ore formation, as well as superimposed syn-metamorphic remobilisation and recrystallization. The primary factors that control the preferred base metal sulphide host of Mn, Fe, Co, Cu, Zn, Ga, As, Se, Ag, Cd, In, Sb, Te, Tl and Bi are element oxidation state, ionic radius of the substituting element, element availability and the maximum trace element budget that a given sulphide mineral can accommodate. Temperature, pressure, redox conditions at time of crystallization and metal source, do not generally appear to influence the preferred base metal sulphide host of all the trace elements. Exceptions are Ga, In and Sn recrystallized at high metamorphic grades, when the preferred host of Ga and Sn usually becomes chalcopyrite. In more typical lower temperature ores, the preferred host of Ga is sphalerite. Indium concentrations also increase in chalcopyrite during recrystallization. At lower temperatures the partitioning behaviour of Sn remains poorly constrained and shows little predictable pattern among the data here. The results obtained may be used as a tool to assess co-crystallization. If trace element distributions in a given base metal sulphide assemblage match those reported here, and assuming those distributions have not been significantly altered post (re-) crystallization, then it may be suggestive of a co-crystallized assemblage. Such information provides a foundation for novel attempts to develop trace element-in-sulphide geothermometers.
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•Trace element partitioning between co-crystallized sulphides is predictable.•Partitioning primarily depends on factors intrinsic to the elements and sulphides.•Partitioning depends little on external factors such as temperature and pressure.•Only high metamorphic conditions affect the partitioning of some elements.
Sphalerite is an important host mineral for a wide range of minor and trace elements. We have used laser-ablation inductively coupled mass spectroscopy (LA-ICPMS) techniques to investigate the ...distribution of Ag, As, Bi, Cd, Co, Cu, Fe, Ga, Ge, In, Mn, Mo, Ni, Pb, Sb, Se, Sn and Tl in samples from 26 ore deposits, including specimens with wt.% levels of Mn, Cd, In, Sn and Hg. This technique provides accurate trace element data, confirming that Cd, Co, Ga, Ge, In, Mn, Sn, As and Tl are present in solid solution. The concentrations of most elements vary over several orders of magnitude between deposits and in some cases between single samples from a given deposit. Sphalerite is characterized by a specific range of Cd (typically 0.2–1.0
wt.%) in each deposit. Higher Cd concentrations are rare; spot analyses on samples from skarn at Baisoara (Romania) show up to 13.2
wt.% (Cd
2+
↔
Zn
2+ substitution). The LA-ICPMS technique also allows for identification of other elements, notably Pb, Sb and Bi, mostly as micro-inclusions of minerals carrying those elements, and not as solid solution. Silver may occur both as solid solution and as micro-inclusions. Sphalerite can also incorporate minor amounts of As and Se, and possibly Au (e.g., Magura epithermal Au, Romania). Manganese enrichment (up to ∼4
wt.%) does not appear to enhance incorporation of other elements. Sphalerite from Toyoha (Japan) features superimposed zoning. Indium-sphalerite (up to 6.7
wt.% In) coexists with Sn-sphalerite (up to 2.3
wt.%). Indium concentration correlates with Cu, corroborating coupled (Cu
+In
3+)
↔
2Zn
2+ substitution. Tin, however, correlates with Ag, suggesting (2Ag
+Sn
4+)
↔
3Zn
2+ coupled substitution. Germanium-bearing sphalerite from Tres Marias (Mexico) contains several hundred ppm Ge, correlating with Fe. We see no evidence of coupled substitution for incorporation of Ge. Accordingly, we postulate that Ge may be present as Ge
2+ rather than Ge
4+. Trace element concentrations in different deposit types vary because fractionation of a given element into sphalerite is influenced by crystallization temperature, metal source and the amount of sphalerite in the ore. Epithermal and some skarn deposits have higher concentrations of most elements in solid solution. The presence of discrete minerals containing In, Ga, Ge, etc. also contribute to the observed variance in measured concentrations within sphalerite.
The classification of the tetrahedrite group minerals in keeping with the current IMA-accepted nomenclature rules is discussed. Tetrahedrite isotypes are cubic, with space group symmetry I4̄3̄m. The ...general structural formula of minerals belonging to this group can be written as M(2)A6M(1)(B4C2)X(3)D4S(1)Y12S(2)Z, where A=Cu+, Ag+, (vacancy), and (Ag6)4+ clusters; B=Cu+, and Ag+; C=Zn2+, Fe2+, Hg2+, Cd2+, Mn2+, Cu2+, Cu+, and Fe3+; D=Sb3+, As3+, Bi3+, and Te4+; Y=S2- and Se2-; and Z=S2-, Se2-, and . The occurrence of both Me+ and Me2+ cations at the M(1) site, in a 4:2 atomic ratio, is a case of valency-imposed double site-occupancy. Consequently, different combinations of B and C constituents should be regarded as separate mineral species. The tetrahedrite group is divided into five different series on the basis of the A, B, D, and Y constituents, i.e., the tetrahedrite, tennantite, freibergite, hakite, and giraudite series. The nature of the dominant C constituent (the so-called "charge-compensating constituent") is made explicit using a hyphenated suffix between parentheses. Rozhdestvenskayaite, arsenofreibergite, and goldfieldite could be the names of three other series. Eleven minerals belonging to the tetrahedrite group are considered as valid species: argentotennantite-(Zn), argentotetrahedrite-(Fe), kenoargentotetrahedrite-(Fe), giraudite-(Zn), goldfieldite, hakite-(Hg), rozhdestvenskayaite-(Zn), tennantite-(Fe), tennantite-(Zn), tetrahedrite-(Fe), and tetrahedrite-(Zn). Furthermore, annivite is formally discredited. Minerals corresponding to different end-member compositions should be approved as new mineral species by the IMA-CNMNC following the submission of regular proposals. The nomenclature and classification system of the tetrahedrite group, approved by the IMA-CNMNC, allows the full description of the chemical variability of the tetrahedrite minerals and it is able to convey important chemical information not only to mineralogists but also to ore geologists and industry professionals.
The Bianjiadayuan Ag-Pb-Zn deposit (4.81 Mt. @157.4 g/t Ag and 3.94% Pb + Zn) is located in the Great Hinggan Range Pb-Zn-Ag-Cu-Mo-Sn-Fe polymetallic metallogenic belt, NE China. Vein type Pb-Zn-Ag ...ore bodies are primarily hosted by slate, adjacent to a Sn ± Cu ± Mo mineralized porphyry intrusion. The deposit is characterized by silver-rich ores with Ag grades up to 3000 g/t. Four primary paragenetic sequences are recognized: (I) arsenopyrite + pyrite + quartz, (II) main sulfide + quartz, (III) silver-bearing sulfosalt + quartz, and (IV) boulangerite + calcite. A subsequent supergene oxidation stage has also been identified. Hydrothermal alteration consists of an early episode of silicification, two intermediate episodes (propylitic and phyllic), and a late argillic episode. Silver mineralization primarily belongs to the late paragenetic sequence III. Freibergite is the dominant and most important Ag-mineral in the deposit. Detailed ore mineralogy of Bianjiadayuan freibergite reveals evidence of chemical heterogeneity down to the microscale. Silver-rich sulfosalts in the late paragenetic sequence III are largely derived from a series of retrograde and solid-state reactions that redistribute Ag via decomposition and exsolution during cooling, illustrating that documentation of post-mineralization processes is essential for understanding silver ore formation. Sulfur and lead isotope compositions of sulfides, and comparison with those of local various geological units, indicate that the ore-forming fluids, lead, and other metals have a magmatic origin, suggesting a close genetic association between the studied Ag-Pb-Zn veins and the local granitic intrusion. Fluid cooling coupled with decreases in
f
O
2
and
f
S
2
are the factors inferred to have led to a decrease of silver solubility in the hydrothermal fluid, and successively promoted extensive Ag deposition.
Minor and trace elements can substitute into the crystal lattice of galena at various concentrations. In situ LA-ICP-MS analysis and trace element mapping of a range of galena specimens from ...different deposit types are used to obtain minor/trace element data, aimed at achieving insight into factors that control minor/trace element partitioning. The previously recognized coupled substitution Ag++(Bi,Sb)3+ ⇌ 2Pb2+ is confirmed. However, the poorer correlation between Ag and (Bi+Sb) when the latter elements are present at high concentrations (∼>2000 ppm), suggests that site vacancies may come into play: 2(Bi,Sb)3++∎ ⇌ 3Pb2+. Galena is the primary host of Tl in all mapped mineral assemblages. Along with Cu, Tl is likely incorporated into galena via the coupled substitution: (Ag,Cu,Tl)++(Bi,Sb)3+ ⇌ 2Pb2+. Tin can reach significant concentrations in galena (>500 ppm). Cd and minor Hg can be incorporated into galena; the simple isovalent substitution (Cd,Hg)2+ ⇌ Pb2+ is inferred. This paper shows for the first time, oscillatory and sector compositional zoning of minor/trace elements (Ag, Sb, Bi, Se, Te, Tl) in galena from two epithermal ores. Zoning is attributed to slow crystal growth into open spaces within the vein at relatively low temperatures.The present data show that galena can host a broader range of elements than previously recognized. For many measured elements, the data sets generated display predictable partitioning patterns between galena and coexisting minerals, which may be dependent on temperature or other factors. Trace element concentrations in galena and their grain-scale distributions may also have potential in the identification of spatial and/or temporal trends within individual metallogenic belts, and as markers of ore formation processes in deposits that have undergone superimposed metamorphism and deformation. Galena trace element geochemistry may also display potential to be used as a trace/minor element vector approach in mineral exploration, notably for recognition of proximal-to-distal trends within a given ore system.
Laser ablation-inductively coupled plasma-mass spectrometry and electron-probe microanalysis were used to investigate the trace-element contents of sphalerite, chalcopyrite and pyrite from the Plaka ...Pb–Zn–Ag deposit. Using petrographic observations, the analytical results could be linked to the temporal evolution of the Plaka ore-forming system. Sphalerite chemistry reliably records the temperature and
f
S
2
evolution of the system, with estimated formation temperatures reproducing the microthermometric results from previous fluid-inclusion studies. Chalcopyrite chemistry also shows systematic variations over time, particularly for Cd, Co, Ge, In, Sn and Zn concentrations. Measurable pyrite was only found in association with early high-temperature mineralisation, and no clear trends could therefore be identified. We note, however, that As and Se contents in pyrite are consistent with formation temperatures estimated from co-existing sphalerite. Statistical analysis of the sphalerite data allowed us to identify the dominant geological controls on its trace-element content. The three investigated factors temperature,
f
S
2
, and sample location account for > 80% of the observed variance in Mn, Fe, Co, Ga, Ge, In, Sb and Hg concentrations, and > 60% of the observed variance in Cd and Sn concentrations. Only for Cu and Ag concentrations is the explained variance < 50%. A similarly detailed analysis was not possible for chalcopyrite and pyrite. Nevertheless, comparison of the results for all three investigated minerals indicates that there are some systematic variations across the deposit which may be explained by local differences in fluid composition.
The large Weilasituo Sn-polymetallic deposit is a recent exploration discovery in the southern Great Xing'an Range, northeast China. The ore cluster area shows horizontal mineralization zoning, from ...the inner granite body outward, consisting of high-T Sn-W-Li mineralization, middle-T Cu-Zn mineralization and peripheral low-T Pb-Zn-Ag mineralization. However, the intrinsic genetic relationship between Sn-W-Li mineralization and peripheral vein-type Pb-Zn-Ag-Cu mineralization, the formation mechanism and the deep geological background are still insufficiently understood. Here, we use fluid inclusions, trace elements concentrations in quartz and sphalerite, and H-O isotope studies to determine the genetic mechanism and establish a metallogenic model. Fluid inclusion microthermometry and Laser Raman spectroscopic analysis results demonstrates that the aqueous ore-forming fluids evolved from low-medium salinity, medium-high temperature to low salinity, low-medium temperature fluids. Laser Raman spectroscopic analysis shows that CH
is ubiquitous in fluid inclusions of all ore stages. Early ore fluids have δ
O
values from + 5.5 to + 6.2‰ and δD values of approximately - 67‰, concordant with a magmatic origin. However, the late ore fluids shifted toward lower δ
O
(as low as 0.3‰) and δD values (~ - 136‰), suggesting mixing between external fluids derived from the wall rocks and a contribution from meteoric water. Ti-in-quartz thermometry indicates a magmatic crystallization temperature of around 700 °C at a pressure of 1.5 kbar for the magmatic ore stage. Cathodoluminescence (CL) imaging and trace element analysis of quartz from a hydrothermal vug highlight at least three growth episodes that relate to different fluid pulses; each episode begins with CL-bright, Al-Li-rich quartz, and ends with CL-dark quartz with low Al and Li contents. Quartz from Episode 1 formed from early Sn-(Zn)-rich fluids which were likely derived from the quartz porphyry. Quartz from episodes 2 and 3 formed from Zn-(Sn)-Cu-rich fluid. The early magmatic fluid is characterized by low fS
. The SO
produced by magma degassing reacted with heated water to form SO
, causing the shift from low fS
to high fS
. The SO
generated was converted to S
by mixing with CH
-rich, Fe and Zn-bearing external fluid which led to late-stage alteration and dissolution of micas in vein walls, thus promoting crystallization of pyrrhotite, Fe-rich sphalerite and chalcopyrite and inhibiting the precipitation of anhydrite. This study shows that ore formation encompassed multiple episodes involving steadily evolved fluids, and that the addition of external fluids plays an important role in the formation of the later Cu-Zn and Ag-Pb-Zn mineralization in the Weilasituo ore district.
•Alkaline sulphide is highly selective for the extraction of antimony and arsenic.•Hypochlorite leaching suffers from high reagent requirements and poor selectivity.•Possible to leach fluorine in ...dilute sulphuric acid both with and without addition of aluminium sulphate.•Pressure oxidative/copper precipitation leaching increases copper grade while simultaneously removing penalty elements.
Custom copper smelters impose substantial financial penalties for the presence of deleterious impurity elements in copper concentrates and can outright reject concentrates which contain impurity elements in concentrations that exceed specified values. Hence, there is strong motivation to remove penalised impurity elements from copper concentrates at the mine site before shipping to custom smelters. A number of leach systems have been developed for the selective extraction of penalty elements from copper concentrates, including: alkaline sulphide leaching (ASL); hypochlorite leaching; dilute sulphuric acid leaching with aluminium sulphate; and combined pressure oxidation (POX) leaching with copper precipitation leaching. This paper reviews these four systems with emphasis on the leaching behaviour of penalty elements. ASL has previously been employed in industry for the selective extraction of As and Sb from tetrahedrite-rich copper concentrates. Sodium sulphide solution leaches As, Sb, and Hg from a large range of minerals, however, does not leach arsenopyrite, a mineral which often contains a significant portion of the total As in copper concentrates. Hypochlorite leaching extracts As associated with enargite minerals. This leach system benefits from superior rates of As extraction when compared with ASL, and for this reason, has gained recent interest within the research community. Two major issues have been identified with hypochlorite leaching of copper concentrates. These are poor reagent selectivity towards As-bearing minerals and high levels of hypochlorite consumption. Unless these two issues are resolved it is unlikely that hypochlorite leaching will be employed in commercial processes. Dilute sulphuric acid leaching with aluminium sulphate is used to extract F associated with fluorite. This leach system also extracts F associated with apatite and chlorite. Laboratory-scale experiments and extensive operating experience have indicated that fluorite can be substantially leached from copper concentrates without addition of aluminium sulphate provided that the concentration of sulphuric acid in the leach solution is sufficiently high (at least 40gL−1). POX/copper precipitation leach systems have potential to extract a large number of penalty elements from copper sulphide concentrates while simultaneously upgrading the concentration of copper in the concentrate. Two patented POX/copper precipitation leach processes have been specifically developed for the deportment of penalty elements. These two processes are reviewed in detail.
The Hillside Cu–(Au) deposit, Yorke Peninsula, South Australia, is a recently-discovered ore system within the 1.6Ga World-class Olympic iron oxide–copper–gold (IOCG) Province. The deposit is ...characterized by a skarn-style alteration zone. Analyses of feldspar, calcite, skarn minerals (garnet, pyroxene, clinozoisite and actinolite) and accessories (titanite, apatite and allanite), and grain-scale element mapping by laser-ablation inductively-coupled plasma mass spectrometry are used to assess the distributions of rare earth element (REE), incompatible and ore-forming elements in host rocks, prograde and retrograde skarn.
Garnet is a major repository of HREE, especially in prograde skarn, whereas LREE-enriched clinozoisite is the principal REE-host in retrograde skarn. REE distribution patterns define a pronounced partitioning of elements among the dominant coexisting minerals. Compositional variation between assemblages, and also within individual grains, defines an evolution from early feldspar–pyroxene skarn through main-stage calcic skarn to the ore-stage. A switch from a prograde, HREE-dominant signature to a LREE-enriched signature is observed in both retrograde and distal skarn. Zr-in-titanite geothermometry supports transition from magmatic to hydrothermal, skarn-forming processes at temperatures of ~660°C; the initiation of ore-stage is about 100°C lower.
Understanding REE distributions in all minerals within a complex, multistage ore system assists the development of vectoring tools that use trace element chemistry in exploration for similar IOCG deposits beneath regolith cover across the Olympic Province. Titanite and apatite show particular promise because of their characteristically distinct REE patterns in magmatic and hydrothermal stages, trace element responses to redox changes, and their widespread abundance throughout different lithologies in the area.
•Trace element signatures are mapped in skarn minerals at the Hillside IOCG deposit.•REY patterns trace the magmatic- to metasomatic evolution of the system.•REY patterns in titanite and apatite show promise as exploration vectors.
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