Malcolm R. Reid

Comparison of digestion methods for ICP-MS determination of trace elements in fish tissues

A comparison is presented of six methods involving nitric acid in conjunction with other reagents to digest three certified marine biological samples (DOLT-3, DORM-3, IAEA-407) and a fish bone homogenate (prepared from Merluccius australis). An inductively coupled plasma-mass spectrometer with an octopole collision cell was used to determine up to 40 elements (Li, B, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Y, Ag, Cd, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, Pb, Th, U) in the digests. These results were assessed in terms of their accuracy and precision, and a flow chart was developed to aid the selection of the optimal digestion method. Although none of the methods was found to give accurate determinations for all elements in the different reference materials, a relatively simple method involving nitric acid and hydrogen peroxide heated in a domestic microwave oven gave the most acceptable results.

The First New Zealanders: Patterns of Diet and Mobility Revealed through Isotope Analysis

Direct evidence of the environmental impact of human colonization and subsequent human adaptational responses to new environments is extremely rare anywhere in the world. New Zealand was the last Polynesian island group to be settled by humans, who arrived around the end of the 13th century AD. Little is known about the nature of human adaptation and mobility during the initial phase of colonization. We report the results of the isotopic analysis (carbon, nitrogen and strontium) of the oldest prehistoric skeletons discovered in New Zealand to assess diet and migration patterns. The isotope data show that the culturally distinctive burials, Group 1, had similar diets and childhood origins, supporting the assertion that this group was distinct from Group 2/3 and may have been part of the initial colonizing population at the site. The Group 2/3 individuals displayed highly variable diets and likely lived in different regions of the country before their burial at Wairau Bar, supporting the archaeological evidence that people were highly mobile in New Zealand since the initial phase of human settlement.

Cyclic voltammetric studies of a thionine coated pyrolytic graphite electrode

Abstract Cyclic voltammetry has been used to study the spontaneous adsorption and oxidative coating of thionine onto basal plane pyrolytic graphite electodes. Spontaneous adsorption leads to a monolayer of flat lying molecules together with some weakly attached upper layers. Oxidation of an adsorbed thionine monolayer results in several products which appear to include polymeric species and the sulphoxide of thionine. Similar products are obtained by an oxidative coating procedure.

Trace metal and major ion concentrations in Lakes Hayes and Manapouri

The major ion (Na+, K+, Mg2+, Ca2+, Sr∗, Cl, SO4 2, alkalinity, reactive Si) and trace metal (Cu, Zn, Fe, Mn, Cd and Pb) compositions of Lakes Hayes and Manapoun have been studied on five occasions throughout the seasonal cycle and depth range of each lake In L Manapoun, seasonal changes in both major element and trace metal concentrations were negligible and almost within the precision of analytical methods, indicating a highly uniform water composition Major element concentrations were extremely low by global standards, in most cases below the 1% percentile level for global fresh waters By contrast, the much shallower L Hayes exhibited much higher major element concentrations, close to the global mean In addition, this lake showed a clear anoxic sub‐surface layer during summer, in which concentrations of the redox‐active metals Fe and Mn became very high Evidence of surface water utilisation of reactive Si, and deeper water scavenging of Cu, were both found in this lake

Does the trace element composition of brown trout Salmo trutta eggs remain unchanged in spawning redds

The temporal stability of trace element concentrations in fertilized, artificially incubated anadromous brown trout Salmo trutta eggs and newly hatched fry was investigated. The anadromous status of the parental fish was confirmed using strontium isotopic analysis of otoliths. Whilst manganese concentrations in eggs varied over time, concentrations of aluminium, potassium, magnesium, strontium, barium and calcium were all unchanged 1 week and 6 weeks post-fertilization as well as in recently hatched larvae. The results clearly suggest that the distinctive trace element signature present in the eggs and newly hatched larvae of anadromous S. trutta (typically characterized by high strontium, low barium) is stable over time. Therefore analysis of the trace element composition of eggs is concluded to be a cost-effective and reliable method for determining the spatial and temporal extent of upstream spawning migration by anadromous salmonids. The temporal variability of at least one element in this study suggests the stability of untested multi-element signatures cannot automatically be assumed.

Iodine Status of New Zealand Elderly Residents in Long-Term Residential Care.

In response to the re-emergence of iodine deficiency in New Zealand, in 2009 the government mandated that all commercially made breads be fortified with iodized salt. There has been no evaluation of the impact of the program on iodine status of the elderly, despite this population group being vulnerable to iodine deficiency or excess. The aim of this study was to describe the iodine status of elderly New Zealanders in residential aged-care homes following the implementation of the bread fortification program. A cross-sectional survey was conducted, involving 309 residents (median age 85 years) from 16 aged-care homes throughout NZ. Information on socio-demographic, anthropometric, dietary and health characteristics were collected. Casual spot urine samples were analysed for urinary iodine concentration (UIC). Blood samples were analysed for serum thyroglobulin, thyroglobulin antibodies, and other biochemical indices. The median UIC (MUIC) of the residents was 72 μg/L, indicating mild iodine deficiency, and 29% had a UIC < 50 μg/L. Median thyroglobulin concentration was 18 ng/mL and 26% had elevated thyroglobulin concentration (>40 ng/mL), suggesting iodine insufficiency. Diuretic use was associated with lower MUIC (p = 0.043). Synthetic thyroxine use was associated with lower odds of having a UIC < 50 μg/L (OR 0.32, p = 0.030)) and lower median thyroglobulin (−15.2 ng/mL, p = 0.001), compared with untreated participants. Frailty was associated with elevated thyroglobulin (p = 0.029), whereas anemia was associated with lower thyroglobulin (p = 0.016). Iodine insufficiency persists in New Zealanders residing in residential aged-care homes despite increasing iodine intake from fortified bread. Research is required to establish optimal iodine intake and status in the elderly.

Implications of Wear at the Titanium-Zirconia Implant- Abutment Interface on the Health of Peri-implant Tissues

PURPOSE To investigate the presence of metallic particles in the peri-implant mucosa around titanium dental implants after 5 years of loading using single-implant crowns with respect to clinical signs of peri-implant inflammation. MATERIALS AND METHODS Sixteen participants from an ongoing, prospective, single-arm clinical trial who had received titanium dental implants restored with single maxillary crowns veneered to zirconia abutments were available for the study. Exfoliative cytology samples were obtained from the peri-implant tissues and contralateral tooth sites using microbrushes and were evaluated by means of light microscopy (LM), scanning electron microscopy, and energy-dispersive spectroscopy (EDS). Trace elemental analysis was also carried out on the microbrushes using inductively coupled plasma mass spectrometry. Peri-implant and periodontal parameters (plaque, bleeding, attachment level, radiographic bone levels) were recorded. RESULTS Titanium particles were found in both the single-implant crown and contralateral natural tooth sites. LM and EDS analyses showed significantly higher numbers of Ti particles at the implant-abutment interfaces (mean = 14.168; SD = 2.36) and in the internal aspects of peri-implant mucosa in contact with the prostheses (mean = 4.438; SD = 2.22) when compared with other test and control areas. Mean probing depths were ≤ 3 mm, and no differences were found in plaque or bleeding on probing between implant and tooth sites. Median bone levels were within the normal range for both implant (mesial: 0.5 mm; distal: 0.8 mm) and tooth (mesial: 1.5 mm; distal: 1.8 mm) sites. CONCLUSION Loading of single-implant zirconia crowns can cause the release of Ti particles because of functional wear at the implant-abutment level. The presence of these metal particles in the peri-implant area did not appear to affect peri-implant health in this patient group.

The origin of plagioclase phenocrysts in basalts from continental monogenetic volcanoes of the Kaikohe-Bay of Islands field, New Zealand: implications for magmatic assembly and ascent

Late Quaternary, porphyritic basalts erupted in the Kaikohe-Bay of Islands area, New Zealand, provide an opportunity to explore the crystallization and ascent history of small volume magmas in an intra-continental monogenetic volcano field. The plagioclase phenocrysts represent a diverse crystal cargo. Most of the crystals have a rim growth that is compositionally similar to groundmass plagioclase (~ An65) and is in equilibrium with the host basalt rock. The rims surround a resorbed core that is either less calcic (~ An20–45) or more calcic (> An70), having crystallized in more differentiated or more primitive melts, respectively. The relic cores, particularly those that are less calcic (< ~ An45), have 87Sr/86Sr ratios that are either mantle-like (~ 0.7030) or crustal-like (~ 0.7040 to 0.7060), indicating some are antecrysts formed in melts fractionated from plutonic basaltic forerunners, while others are true xenocrysts from greywacke basement and/or Miocene arc volcanics. It is envisaged that intrusive basaltic forerunners produced a zone where various degrees of crustal assimilation and fractional crystallization occurred. The erupted basalts represent mafic recharge of this system, as indicated by the final crystal rim growths around the entrained antecrystic and xenocrystic cargo. The recharge also entrained cognate gabbros that occur as inclusions, and produced mingled groundmasses. Multi-stage magmatic ascent and interaction is indicated, and is consistent with the presence of a partial melt body in the lower crust detected by geophysical methods. This crystallization history contrasts with traditional concepts of low-flux basaltic systems where rapid ascent from the mantle is inferred. From a hazards perspective, the magmatic system inferred here increases the likelihood of detecting eruption precursor phenomena such as seismicity, degassing and surface deformation.

Predictors of pesticide concentrations in freshwater trout - The role of life history.

Concentrations of halogenated pesticides in freshwater fish can be affected by age, size, trophic position, and exposure history. Exposure history may vary for individual fish caught at a single location due to different life histories, e.g. they may have hatched in different tributaries before migrating to a specific lake. We evaluated correlations of pesticide concentrations in freshwater brown trout (Salmo trutta) from the Clutha River, New Zealand, with potential predictors including capture site, age, length, trophic level, and life history. Life history was determined from otolith (fish ear bone) strontium isotope signatures, which vary among tributaries in the region of our study. Variability in pesticide concentrations between individual fish was not well explained by capture site, age, length, or trophic level. However, hexachlorobenzene (HCB) and chlorpyrifos concentrations were distinct in lake-based trout with different life histories. Additionally, one of the riverine life histories was associated with relatively high concentrations of total endosulfans. Linear models that included all potential predictor variables were evaluated and the resulting best models for HCB, chlorpyrifos, and total endosulfans included life history. These findings show that in cases where otolith isotope signatures vary geographically, they can be used to help explain contaminant concentration variations in fish caught from a single location.

Effect of a cordless retraction paste on titanium surface: a topographic, chemical and biocompatibility evaluation

Good exposure of the preparation margins and haemostasis in the sulcular gingiva are necessary for accurate impressions to produce precise restorations. The use of cordless retraction paste material in implant dentistry is a relatively novel application. However, few studies have been conducted on the use of retraction pastes and their possible interaction with implant surfaces. Recent literature has described remnants on titanium implant surfaces and expressed the need for an assessment of the biocompatibility of the exposed surface (Chang et al.). This in vitro study evaluated the effect of a cordless gingival retraction paste on sterile titanium disks. Surface chemistry was determined using energy-dispersive X-ray spectroscopy (EDS), and further investigated using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). After exposure to retraction paste, surface chemistry alterations were identified. A fibroblast cell line (L929) was exposed to the disks and the live/dead viability/cytotoxicity assay was used to determine any effects on the proliferation and health of cells. The disks exposed to the retraction paste showed fewer dead cells compared to the unexposed disks. This was statistically significant.