Norman M. Halden

Oscillatory zinc distribution in Arctic char (Salvelinus alpinus) otoliths:: The result of biology or environment?

Scanning proton microprobe (SPM) analysis and imaging was used to map the distribution of zinc in otoliths of anadromous and non-anadromous Arctic char (Salvelinus alpinus) from the Canadian Arctic. Zinc distribution patterns were oscillatory with concentrations ranging from 35 to 240 ppm. Superimposition of the zinc distribution on optical images of the otoliths permitted correlation of zinc uptake with annular structure in the otoliths and with strontium patterns from the same otolith. Well defined oscillations of zinc concentrations were observed in the otoliths, particularly in the first few years in all samples. In anadromous fish, these overlapped with the onset of the strontium oscillations that were indicative of anadromy and then declined; in non-anadromous fish the oscillations generally continued to later years. Oscillatory zoning of zinc may indicate: (1) variations in the concentration of zinc in water; (2) variations in nutrient availability in the environment; (3) temperature variations in the habitat occupied; or (4) a combination of zinc concentration, nutrient availability or temperature changes. As such, the systematic distribution of zinc in otoliths has the potential to provide temporally constrained information on fish habitat and/or fish biology.

Scanning proton microprobe analysis of strontium in an arctic charr, Salvelinus alpinus, otolith: implications for the interpretation of anadromy

SynopsisScanning proton microprobe imaging has been used to map the distribution of strontium (Sr) in an arctic charr, Salvelinus alpinus, otolith. X-ray maps show that Sr variation follows an oscillatory zoned pattern which correlates with optically resolved zones (annuli). The internal region of the otolith shows optical zonation but no significant Sr content. Comparison of the optical image with the Sr X-ray map provides evidence of when the fish entered a high Sr environment. This may be interpreted as when the fish migrated from fresh water to a marine environment; this particular fish first migrated to sea in its eighth year. Micro-PIXE point analysis was used to determine the abundance of Sr in annuli along a radius from the nucleus to an outer edge; Sr levels in the internal region were about 10 ppm and variation in the outer zoned region was between 62 and 175 ppm. Detection limits for Sr are in the 1–2 ppm range. Other trace elements, such as transition elements, were found to be present in some growth regions in the 1–20 ppm range. Proton beam analysis is a non-destructive analytical technique capable of preserving the spatial integrity of trace-element data in otoliths such that element distribution may be linked to the growth structure of the otolith.

Trace-element distributions in fish otoliths: natural markers of life histories, environmental conditions and exposure to tailings effluence

Abstract Otoliths, the earbones of teleost (bony) fish, are constructed from alternating layers of aragonite and protein. Laser ablation inductively coupled plasma mass spectrometry and proton-induced X-ray emission are used to obtain spatially well-resolved trace element line-scans that show trace-element concentrations are correlated with the annular structure. Zoned Sr and Zn signatures are common whereas other elements such as Cu, Pb, Li and Cs can be related to the proximity of mineral deposits. Aragonite in otoliths can incorporate a wide range of trace elements at the low-ppm level including alkali- and alkaline-earth elements and base metals; Se has also been detected in proximity to coal mines. These trace elements, in combination with the annular structures, are an important archive for recording information on environments occupied by fish, environmental change and exposure to pollutants.

MICRO-PIXE STUDIES OF SR ZONING IN ARCTIC CHARR OTOLITHS : MIGRATORY BEHAVIOUR AND STOCK DISCRIMINATION

Abstract Micro-PIXE has been used to determine the content of strontium in the growth zones of Arctic charr otoliths. A well-defined correspondence is observed between the optically observed growth zones and the strontium zoning pattern. Line-scan data indicate whether or not the fish concerned is anadromous, and they define the years in which migration to the sea has taken place; they also are sensitive to the geographic origin of the fish. These results suggest that micro-PIXE can be a useful tool in the management and conservation of the Arctic charr.

Micro-PIXE analysis of trace element variation in otoliths from fish collected near acid mine tailings: Potential for monitoring contaminant dispersal

Abstract Otoliths from fish sampled proximal to acid mine tailings located near Sherridon, Manitoba contain elevated abundances of Zn, Mn, Fe and Cu. Sr is also present in amounts ranging from 250 to 1200 ppm with the actual levels dependent on the lake from which fish were taken. Previous work on analyzing Zn and Mn suggests Zn will typically vary between 50 and ∼100 ppm (in marine and non-marine species) and Mn between 10 and ∼100 ppm. Otoliths analyzed in this study contain up to ∼1000 ppm Zn and up to ∼400 ppm Mn; Fe is present, ranging between 50 and 100 ppm and Cu is typically 40–50 ppm. Water samples showed variation in these elements depending on proximity to the tailings.

Micro-PIXE studies of char populations in northern Canada

Abstract Micro-PIXE analysis of trace elements in otoliths has been used as the basis for several projects on char, a fish that is important for aboriginal subsistence fisheries in Arctic Canada. Life-history patterns were originally inferred from micro-PIXE line scans of Sr distribution. These were confirmed by superposition of Sr distribution patterns on optical images of otoliths of tag-recaptured fish. Char from various populations showed differentiation in otolith primordial Sr concentration; this enables us to differentiate biological stocks and, it is hoped, eventually to assign individuals from mixed-stock fisheries to their stock of origin. Zn oscillations also correlate with annular structure and provide additional temporally constrained information on fish habitat and behaviour.

PIXE and micro-PIXE analysis of minerals at Ep = 40 MeV

Abstract Proton-induced X-ray emission (PIXE) analysis has been employed at the University of Manitoba Accelerator Centre in the analysis of apatite samples containing trace amounts of rare earth elements (REE). Detection limits of 5 ppm or better were readily achieved for elements such as La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy and Yb. Qualitative results of an analysis of Durango apatite were compared with the published results of other authors and found to be in general agreement. The relative ease with which results might be extracted from K X-ray data obtained for medium to high Z elements studied at the energy of the Manitoba accelerator is contrasted with data reduction techniques employed at lower energy PIXE facilities.

Validation of Oligohaline Elemental Otolith Signatures of Striped Bass by Use of In Situ Caging Experiments and Water Chemistry

Abstract The spatiotemporal variability in strontium (Sr), barium (Ba), magnesium (Mg), and manganese (Mn) elemental signatures of water and fish otoliths was assessed from July to October 2008 across river habitats of Albemarle Sound, North Carolina. We examined whether relationships in these signatures exist and the potential of otoliths to serve as innate chemical tags. Hatchery-reared age-0 striped bass Morone saxatilis were placed in cages at four different locations to test development of habitat-specific otolith signatures. Dissolved elemental water and otolith signatures exhibited spatial variability but did not vary temporally. Chemical water signatures classified habitats with 76–81% accuracy, and otolith signatures of caged fish displayed 59–63% total classification accuracy depending on the classification method used. The elements Sr, Ba, and Mn were the main habitat discriminators, as their concentrations in otoliths were significantly correlated with concentrations in the water. Otolith Mg was not related to water chemistry and did not vary among habitats. Natural physiochemical gradients, geochemical processes, and possibly anthropogenic inputs influenced the trace elemental signatures of Albemarle Sound habitats. The unique chemical signals of the sounds river habitats validate the use of otolith signatures for determining striped bass habitat utilization in this system. Use of otolith elemental signatures as natural tags provides a quantitative method to determine the proportion of juvenile striped bass recruiting to the adult spawning stock from specific habitats, thus aiding resource managers in identifying habitats that should receive priority in restoration and conservation decisions.

Determining exposure history of northern pike and walleye to tailings effluence using trace metal uptake in otoliths.

Determining the effects of mining activity on fish populations is complicated by the uncertainty of fish residency in an affected area. Otoliths are considered to be metabolically inert and can contain complete chemical records of environments in which individuals have lived. When coupled with the annular structure, otoliths provide temporal information to the history of exposure to pollutants. In this preliminary study, northern pike and walleye otoliths collected from two lakes adjacent to base metal mine tailings at Lynn Lake, Manitoba, Canada, were analyzed using laser ablation inductively coupled plasma mass spectrometry to determine background levels of trace metals. The presence of overlapping Zn, Cu, and Pb peaks above background levels in some otoliths is interpreted as a record of elevated levels in the environment. These otoliths provided a record of the history of fish movement into and out of the affected area.

Micro-PIXE analysis of strontium in Arctic char, Salvelinus alpinus, otoliths from Quttinirpaaq National Park, Nunavut, Canada

Abstract Arctic char, Salvelinus alpinus, exhibit either lake resident or anadromous (sea-run) life histories. Anadromy is less prevalent at the northern and southern extremes of the distribution. Effective conservation and management of char requires knowledge of life histories exhibited by individuals and populations. Micro-PIXE line-scans were used to determine the distribution of strontium (Sr) in otoliths from which life history patterns were determined for Arctic char from 10 lakes in Quttinirpaaq National Park in the Canadian High Arctic. Although most populations were lake resident as expected, the data indicated that a component of the char population from one lake was anadromous. This represents the most northerly known char population to exhibit anadromy. Mean Sr concentrations in otoliths of char from all populations, as determined by point analysis and also from line-scan data, showed no significant differences between the methods. Mean Sr concentrations (from point analysis) showed significant differences between some of the populations. These differences combined with other analyses (e.g. morphometrics, genetics) can be used to differentiate biological populations. Thus, micro-PIXE analysis is a useful tool for assessing diversity in Arctic char and contributing to their management and conservation in the park.