Professor Neil Ward PhD FRSC

The effect of vacuum exposure on latent fingerprint chemistry has been evaluated. Fingerprints were analysed using a quartz crystal microbalance to measure changes in mass, gas chromatography mass spectrometry to measure changes in lipid composition and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) to determine changes in the content of water, fatty acids and their esters after exposure to vacuum. The results are compared with samples aged under ambient conditions. It was found that fingerprints lose around 26% of their mass when exposed to vacuum conditions, equivalent to around 5 weeks ageing under ambient conditions. Further exposure to vacuum causes a significant reduction in the lipid composition of a fingerprint, in particular with the loss of tetradecanoic and pentadecanoic acid, that was not observed in ambient aged samples. There are therefore implications for sequence in which fingerprint development procedures (for example vacuum metal deposition) are carried out, as well as the use of vacuum based methods such as secondary ion mass spectrometry (SIMS) and matrix-assisted laser desorption ionisation (MALDI) in the study of fingerprint chemistry. © 2013 .

A novel dibenzo-18-crown-6 ether (DB-18CE-6)- functionalised silica (SiO2) disk was found to be a capable source preparation technique for the rapid analysis of 226Ra by alpha-spectrometry. DB-18CE-6 was chemically immobilised onto the surface of SiO2 disks. It is anticipated that the high levels of selectivity of DB-18CE-6 for radium will allow for an efficient chemical separation of 226Ra from other elements present in sample matrices. 226Ra was adsorbed as a monolayer onto the surface of the silica disks, attaching to the functionalised centres of the DB-18CE-6 structure, forming a high resolution counting source for alpha-spectrometry. The chemical recovery of radium from synthetic samples was 2.3% at pH 2, with higher recoveries expected over the pH range of 4−10.

Soil and water samples were collected from farmsteads and provincial towns across the provinces of La Pampa and San Juan in Argentina. Inductively coupled plasma mass spectrometry was used for the determination of iodine in water following addition of TMAH to 1% v/v and soils extracted with 5% TMAH. Iodine in agricultural soils was in the range of 1.3–20.9 mg/kg in La Pampa located in central Argentina and 0.1–10.5 mg/kg in San Juan located in the northwest Andean region of Argentina, compared to a worldwide mean of 2.6 mg/kg. Mean selenium concentrations for soils from both provinces were 0.3 mg/kg, compared to a worldwide mean of 0.4 mg/kg. The majority of soils were slightly alkaline at pH 6.7 to 8.8. The organic content of soils in La Pampa was 2.5–5.9% and in San Juan 0.1–2.3%, whilst, mobile water extractable soil-iodine was 1–18% for La Pampa and 2–42% for San Juan. No simple relationship observed for pH and organic content, but mobile iodine (%) was highest when organic content was low, higher for lower total iodine concentrations and generally highest at pH > 7.5. Water drawn for drinking or irrigation of a variety of crops and pasture was found to range from 52 to 395 µg/L iodine and 0.8 to 21.3 µg/L selenium in La Pampa and 16–95 µg/L iodine and 0.6 to 8.2 µg/L selenium in San Juan. The water samples were all slightly alkaline between pH 8 and 10. Water–iodine concentrations were highest at pH 7.8 to 8.8 and in groundwaters positively correlated with conductivity. Raw water entering water treatment works in La Pampa was reduced in iodine content from approximately 50 µg/L in raw water to 1 µg/L in treated drinking water, similar to levels observed in regions experiencing iodine deficiency.

The arsenic speciation analysis of ground water was undertaken in southern La Pampa and Buenos Aires provinces of Argentina. These regions have been reported to have high levels of arsenic in waters resulting from the layers of volcanic ash within the Chaco-Pampean plain. Forty wells were sampled adjacent to ruta 35 between San Martin (La Pampa) and San German (Buenos Aires). A field-based method utilising solid phase extraction cartridges enabled the selective retention of iAsIII, iAsV, MAV and DMAV. All fractions and a ‘total’ arsenic AsT acidified sample were analysed by ICP-MS using a collision cell. Total arsenic levels varied from 23.0 to 289.0 μg L-1, with the highest levels in La Pampa. Urban well waters from San Martin and San German were well above the World Health Organisation (WHO) guidelines for drinking water (10 μg L-1 AsT). Speciation levels varied depending on province, type of well, conductivity and redox potential (Eh); but not pH. In this study for rural wells arsenite (iAsIII) was the predominant species, whereas for urban wells in Buenos Aires it was arsenate iAsV.

Surface water originating from the Copahue volcano crater-lake was analysed for total arsenic and four arsenic species: arsenite (iAs(III)), arsenate (iAs(V)), monomethylarsonic acid (MA(V)) and dimethylarsinic acid (DMA(V)) and other trace elements (Fe, Mn, V, Cr, Ni, Zn). A novel in-field technique for the preconcentration and separation of four arsenic species was, for the first time, used for the analysis of geothermal and volcanic waters. Total arsenic levels along the río Agrio ranged from

Contamination of groundwater with arsenic from natural sources is endemic in the West Bengal region of India. Despite increased awareness regarding the consumption of safe water for drinking, the use of groundwater for agricultural purposes, cooking and other domestic tasks still prevails. This study investigates the accumulation of As, Mn and Fe in paddy soils irrigated with groundwater and evaluates the levels of these elements in the different parts of the rice plants. The results show that although there is a significant accumulation of As, Mn and Fe in the soils irrigated with groundwater, the uptake by the grains is not proportional to the concentrations in the soils. Arsenic is accumulated mainly in the roots, followed by straw and grains, and significant amounts of arsenic are removed by de-husking of the rice (86–88 % of As in the wholegrain). The evaluation of the effect of washing and cooking the rice with groundwater shows that there is a marked increase in the arsenic levels of cooked rice (up to 232 %). However, the accumulation is highly dependent on the type of rice, with processed commercial samples (parboiled) having a lower capacity to retain arsenic than the rice varieties utilised by the local villagers.

Chemical composition analysis of açaí extracts revealed higher levels of total polyphenol content in purple açaí samples for both commercial (4.3–44.7 gallic acid equivalents mg/g) and non-commercial samples (30.2–42.0 mg/g) compared to white (8.2–11.9 mg/g) and oil samples (0.8–4.6 mg/g). The major anthocyanin compounds found in purple açaí samples were cyanidin-3-glucoside and cyanidin-3-rutinoside with total concentrations in the range of 3.6–14.3 cyanidin-3-glucoside equivalents mg/g. The oligomeric proanthocyanidins were quantified in the range of 1.5–6.1 procyanidin B1 equivalents mg/g. Moreover, açaí presented significant levels of calcium, magnesium, manganese, iron, zinc and copper, essential minor and trace elements, in comparison with other berries. All of the açaí extracts at 50 μg/mL potently inhibited the release of reactive oxygen species in lipopolysaccharide-stimulated RAW 264.7 murine macrophage cells, but none inhibited the release of nitric oxide. Furthermore, all the açaí samples demonstrated potential as wound healing agents due to the high levels of migration activity in human fibroblast cells.

A novel dibenzo-18-crown-6 ether (DB-18CE-6)- functionalised silica (SiO2) disk was found to be a capable source preparation technique for the rapid analysis of 226Ra by alpha-spectrometry. DB-18CE-6 was chemically immobilised onto the surface of SiO2 disks. It is anticipated that the high levels of selectivity of DB-18CE-6 for radium will allow for an efficient chemical separation of 226Ra from other elements present in sample matrices. 226Ra was adsorbed as a monolayer onto the surface of the silica disks, attaching to the functionalised centres of the DB-18CE-6 structure, forming a high resolution counting source for alpha-spectrometry. The chemical recovery of radium from synthetic samples was 2.3% at pH 2, with higher recoveries expected over the pH range of 4−10.

The human body requires certain amount of trace elements to function properly (especially those that are classified as essential to health). Most elements are co-factors in the molecular mechanisms within the body but when in excess can also cause toxicity. Concentrations of some elements in excess (above optimum) or deficient amount can progress to some types of metabolic abnormalities which could lead to obesity. Obesity is a multifactorial condition with multiple pathways including environmental, dietary, and genetic. All these factors, including elemental abnormalities can disrupt the molecular mechanisms. Whilst there is evidence that obesity causes several elemental deficiencies, there is lack of knowledge on how these elemental deficiencies are related to an obese individual. This review examined the literature to determine if there are biological reasons to believe that low or increased concentrations of certain trace elements, namely, copper, magnesium, iodine, cobalt, molybdenum, boron, antimony, aluminium, chromium, selenium, manganese, calcium, zinc and iron might be associated with increased body fat.

Inductively coupled plasma mass spectrometry (ICP-MS) was used to quantify the total amount of trace elements in retina from adult male Sprague-Dawley rats (n = 6). Concentration of trace elements within individual retinal areas in frozen sections of the fellow eye was established with the use of two methodologies: (1) particle-induced X-ray emission (PIXE) in combination with 3D depth profiling with Rutherford backscattering spectrometry (RBS) and (2) synchrotron X-ray fluorescence (SXRF) microscopy. The most abundant metal in the retina was zinc, followed by iron and copper. Nickel, manganese, chromium, cobalt, selenium and cadmium were present in very small amounts. The PIXE and SXRF analysis yielded a non-homogenous pattern distribution of metals in the retina. Relatively high levels of zinc were found in the inner part of the photoreceptor inner segments (RIS)/outer limiting membrane (OLM), inner nuclear layer and plexiform layers. Iron was found to accumulate in the retinal pigment epithelium/choroid layer and RIS/OLM. Copper in turn, was localised primarily in the RIS/OLM and plexiform layers. The trace elements iron, copper, and zinc exist in different amounts and locations in the rat retina.

Arsenic, copper and lead metals are serious contaminants for human health. These metals are all toxic above a minimum concentration. In the present study twenty two water samples (eleven sites - non and acidified) from villages Nea Silata, Nea Triglia, Eleochoria, Nea Plagia, Tenedos and Sozopolis, municipality of Poligiros, prefecture of Chalkidiki, Greece were collected for quantitatively determination of arsenic, copper-65 and lead-208 by Hydride Generation - Atomic Absorption Spectroscopy (HG-AAS) and Inductively Coupled Plasma - Mass Spectrometry (ICP-MS). The kinds of water were categorized as: drinking water, irrigation water and geothermal water. The results exhibited normal levels for all the three heavy metals under examination apart from geothermal water at Eleochoria village and in some cases for irrigation water at Nea Triglia and Tenedos villages for which the levels of arsenic were a little elevated. Drinking water samples from Nea Plagia and Nea Triglia villages showed lower heavy metal levels than the official Maximum Contaminant Levels (MCL) and therefore the water at these villages is considered to be potable.

Water from La Pampa, Argentina, was used for washing and cooking rice to examine the in-situ impact of using naturally-contaminated water for food preparation on the elemental dietary intake. Whilst washing with the control tap water (28 g/L As) reduced the concentration of As in rice by 23%, the use of different well waters (281-1144 g/L) increased As levels significantly (48-227%) in comparison with the original concentration in the rice (0.056 µg/g). Cooking the rice at a low water-to-rice ratio (2:1) using modern methods increased the levels of As in the cooked samples by 2-3 orders of magnitude for both pre-washed and un-washed rice. Similar trends were observed for vanadium. Although the levels of manganese, iron, copper, zinc and molybdenum in rice were reduced during washing and cooking for most water samples, the molybdenum concentration in the cooked rice doubled (2.2-2.9 µg/g) when using water containing >1 mg/L Mo.

The effect of competing ions on the sorption behaviour of uranium onto carboxyl-functionalised graphene oxide (COOH-GO) were studied in batch experiments in comparison to graphene oxide (GO) and graphite. The effect of increasing the abundance of select chemical functional groups, such as carboxyl groups, on the selectivity of U sorption was investigated. In the course of the study, COOH-GO demonstrated superior performance as a sorbent material for the selective removal of uranyl ions from aqueous solution with a distribution coefficient of 3.72 ± 0.19 × 103 mL g−1 in comparison to 3.97 ± 0.5 × 102 and 2.68 ± 0.2 × 102 mL g−1 for GO and graphite, respectively.

Some regions of Argentina are affected by high concentrations of molybdenum, arsenic and vanadium from natural sources in their groundwater. In particular, Mo levels in groundwater from Eduardo Castex (La Pampa, Argentina) typically exceed the guidelines for drinking water formerly established by WHO at 70 μg/L. Therefore, this study investigated the uptake of Mo in plants, using cress ( Lepidium sativum L . ) as a model using hydroponic experiments with synthetic solutions and groundwater from La Pampa. Cress grown from control experiments (150 μg/L Mo, pH 7) presented an average Mo concentration of 35.2 mg/kg (dry weight, d.w.), higher than the typical total plant range (0.7–2.5 mg/kg d.w.) in the literature. Using pooled groundwater samples (65.0–92.5 μg/L Mo) from wells of La Pampa (Argentina) as growth solutions resulted in significantly lower cress Mo levels (1.89–4.59 mg/kg d.w.) than were obtained for synthetic solutions of equivalent Mo concentration. This may be due to the high levels in these groundwater samples of As, V, Fe and Mn which are known to be associated with volcanic deposits. This research addressed the hitherto scarcity of data about the effect of various physicochemical parameters on the uptake of Mo in plants.

Behavioral problems are multifactorial and includes perinatal, maternal, family, parenting, socio-economic and personal risk factors, but less is known about the association of postnatal heavy metals on children’s behavioral problems in Pacific Island children. Methods: A cohort of eligible nine-year-old children within a Pacific Island Families longitudinal study were recruited for a cross-sectional study. Child behavior problems were assessed using the child behavior checklist. Heavy metals (including Ni, Cu, Pb, Al, Cr and Cd) were determined in toenails, after acid digestion and analyzed using inductively coupled plasma mass spectrometry. Other factors such as lifestyle (smoking in pregnancy), health outcomes (obesity, health status), demographics (gender, ethnicity, parents’ marital status) and socioeconomic status (household income levels) were also collected. The statistical analysis included t-tests for independent sample and Mann–Whitney U-test, and chi-square or Fisher’s exact tests of independence for comparisons of the proportions. Regression models tested the hypothesized risk factors for behavior outcomes. Results: This observational study enrolled 278 eligible Pacific Island children living in Auckland, New Zealand. The prevalence of behavioral problems in the clinical range was high (22%) but there was no significant association between heavy metals in toenails and adverse behavioral outcomes. Conclusion: Regular monitoring and assessments of children for environmental risk factors, as well as social and lifestyle factors for behavior problems, continues. Alternative indicators of exposure to heavy metal should be evaluated.

Banana peels were used as feedstock to produce a carbon dense hydrochar for the removal of toxic metals from wastewater. Compared to the biomass feedstock (41.3% mass C), the banana peel hydrochar possesses higher carbon (54–72% mass C) and lower ash contents. The carbonised banana peels treated between 150 and 300 °C (1−2h) demonstrated an excellent ability to remove Cd2+ (5–100 mg L−1), achieving 99% removal, in comparison with 75% for the raw peel. The liquid by-product generated in the carbonisation process was tested as feedstock in microbial electrochemical devices, showing significant reduction in the chemical oxygen demand levels (initially 10–25 103 mg L−1), associated with the production of electrical outputs; 81–85% reduction with microbial communities from compost, and 53–85% with anaerobic sludge. The results demonstrate the complete utilization of waste from mass cultivation of banana, providing a full-cycle solution for the pollution associated to this important crop. [Display omitted] •Hydrothermal carbonisation is a sustainable solution for waste in banana industry.•Hydrochars from banana peels are effective sorbents of Cd2+ ion from water.•Promising use of liquid by-product from hydrocharring for bioelectrochemical cells.

This is the industry and government standard and was introduced to address the common causes of project failure i.e. not delivering projects on time, within budget, within scope or to the right quality.

There is limited evidence on the distribution of heavy metals and its association with secondhand smoking (SHS) within Pacific Island children living in New Zealand. Certain heavy metals such as cadmium (Cd), lead (Pb), and aluminum (Al) bioaccumulates in the body and can deteriorate health in both children and adults. Others, such as chromium (Cr) and nickel (Ni) in trace amounts are necessary but become toxic at high levels. Exposure routes of these elements include food, water, and air. The purpose of this study was to identify the distribution of toxic metal concentrations and its possible correlation with SHS within the Pacific Island children. A sub-sample of children within Pacific Island families longitudinal study, at the nine-year phase, who were living in the New Zealand city of Auckland were invited to participate, (n = 278). Toenails were used as a biomarker to determine Cr, Pb, Cd, Cu, Ni, and Al concentration using inductively coupled plasma mass spectrometry. Reliable and validated questionnaires were used for demographics, lifestyle, and health outcome variables. Significant differences between household smoking status and ethnicity, as well as parents’ marital status, were observed (p < 0.05). There was no statistical difference in heavy metal concentrations in smoking versus non-smoking households. However, Cr, Pb, Cd, Cu, and Ni concentrations were all higher than the required optimal health value in both groups. A high concentration of heavy metals was observed in these children that exceeded the value required for optimal health, although no significant difference in heavy metals with regards to secondhand smoking was observed. SHS was associated with children’s ethnicity and parental marital status, but not with household income levels or maternal education.

Imaging and analyzing gunshot residue (GSR) particles using the scanning electron microscope equipped with an energy dispersive X-ray spectrometer (SEM-EDS) is a standard technique that can provide important forensic evidence, but the discrimination power of this technique is limited due to low sensitivity to trace elements and difficulties in obtaining quantitative results from small particles. A new, faster method using a scanning proton microbeam and Particle Induced X-ray Emission (μ-PIXE), together with Elastic Backscattering Spectrometry (EBS) is presented for the non-destructive, quantitative analysis of the elemental composition of single GSR particles. In this study, the GSR particles were all Pb, Ba, Sb. The precision of the method is assessed. The grouping behaviour of different makes of ammunition is determined using multivariate analysis. The protocol correctly groups the cartridges studied here, with a confidence >99%, irrespective of the firearm or population of particles selected.

Acai consumption has been increasing due to the health benefits associated with the levels of essential elements and bioactive compounds, such as phenols and flavonoids. However, any nutritional information needs to go beyond that for total elemental levels, and elemental bioaccessibility data for this food should also be highlighted. In this study, the bioaccessibility of essential elements in two different genotypes of acai pulp (white and purple) was evaluated. The in vitro gastrointestinal digestion of acai pulp followed by elemental determination using inductively coupled plasma optical emission spectrometry (ICP OES) was performed to evaluate the bioaccessibility of Ca, Cu, Fe, K, Mg, Mn, P, and Zn. The total elemental concentrations for purple and white acai pulp were found to not be significantly different between the genotypes. Most of the elements studied showed high levels of bioaccessibility, with values greater than 70%, apart from Fe in purple acai, which had the lowest bioaccessibility level.

Acai fruit is recognized for its health promoting properties. However, there is still a need to address the effects of industrial processing on this fruit. In this study, phenolic content, anti-inflammatory properties and dermal wound repair properties of 20 acai samples, before and after industrial processing, from various Amazon regions were investigated. Acai pulp was rich in total phenolics (18.9–58.8 mg g−1) and proanthocyanins (9.8–43.1 mg g−1), but contained trace anthocyanins (up to 0.1 mg g−1). Industrially processed samples lost substantial amounts of proanthocyanidins (up to 83.2%), while the anthocyanins inherently present were greatly enriched after processing (20-fold higher). Non-processed acai pulp extracts protected against early inflammation response which was correlated with proanthocyanidins, by significantly inhibiting nitric oxide production and suppressing pro-inflammatory gene expression including interleukin-1β, cyclooxygenase-2, nitric oxide synthase, and interleukin-6. The promotion of dermal wound repair of acai seed and pulp extracts was mainly contributed by anthocyanins and other bioactive compounds. The anti-inflammatory effect was diminished but wound healing effect was retained after pulp processing, suggesting the processing technology needs to be improved to maintain biological properties of acai fruit.

A new protocol using time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been developed to identify the deposition order of a fingerprint overlapping an ink line on paper. By taking line scans of fragment ions characteristic of the ink molecules (m/z 358.2 and 372.2) where the fingerprint and ink overlap and by calculating the normalised standard deviation of the intensity variation across the line scan, it is possible to determine whether or not a fingerprint is above ink on a paper substrate. The protocol adopted works for a selection of fingerprints from four donors tested here and for a fingerprint that was aged for six months; for one donor, the very faint fingerprints could not be visualized using either standard procedures (ninhydrin development) or SIMS and therefore the protocol correctly gives an inconclusive result.

The arsenic speciation analysis of water (surface and ground) was undertaken in thirteen provinces of Argentina. A field-based method utilizing solid phase extraction cartridges enabled the selective retention of iAs III, iAsV, MAV and DMAV. All fractions and a 'total' arsenic acidified sample were analyzed by ICP-MS using a collision cell. Total arsenic levels varied from

Arsenic (As) speciation in surface and groundwater from two provinces in Argentina (San Juan and La Pampa) was investigated using solid phase extraction (SPE) cartridge methodology with comparison to total arsenic concentrations. A third province, Rio Negro, was used as a control to the study. Strong cation exchange (SCX) and strong anion exchange (SAX) cartridges were utilised in series for the separation and preservation of arsenite (As-III), arsenate (As-V), monomethylarsonic acid (MA(V)) and dimethylarsinic acid (DMA(V)). Samples were collected from a range of water outlets (rivers/streams, wells, untreated domestic taps, well water treatment works) to assess the relationship between total arsenic and arsenic species, water type and water parameters (pH, conductivity and total dissolved solids, TDS). Analysis of the waters for arsenic (total and species) was performed by inductively coupled plasma mass spectrometry (ICP-MS) in collision cell mode. Total arsenic concentrations in the surface and groundwater from Encon and the San Jos, de Jachal region of San Juan (north-west Argentina within the Cuyo region) ranged from 9 to 357 mu g l(-1) As. Groundwater from Eduardo Castex (EC) and Ingeniero Luiggi (LU) in La Pampa (central Argentina within the Chaco-Pampean Plain) ranged from 3 to 1326 mu g l(-1) As. The pH range for the provinces of San Juan (7.2-9.7) and La Pampa (7.0-9.9) are in agreement with other published literature. The highest total arsenic concentrations were found in La Pampa well waters (both rural farms and pre-treated urban sources), particularly where there was high pH (typically > 8.2), conductivity (> 2,600 mu S cm(-1)) and TDS (> 1,400 mg l(-1)). Reverse osmosis (RO) treatment of well waters in La Pampa for domestic drinking water in EC and LU significantly reduced total arsenic concentrations from a range of 216-224 mu g l(-1) As to 0.3-0.8 mu g l(-1) As. Arsenic species for both provinces were predominantly As-III and As-V. As-III and As-V concentrations in San Juan ranged from 4-138 mu g l(-1) to < 0.02-22 mu g l(-1) for surface waters (in the San Jos, de Jachal region) and 23-346 mu g l(-1) and 0.04-76 mu g l(-1) for groundwater, respectively. This translates to a relative As-III abundance of 69-100% of the total arsenic in surface waters and 32-100% in groundwater. This is unexpected because it is typically thought that in oxidising conditions (surface waters), the dominant arsenic species is As-V. However, data from the SPE methodology suggests that As-III is the prevalent species in San Juan, indicating a greater influence from reductive processes. La Pampa groundwater had As-III and As-V concentrations of 5-1,332 mu g l(-1) and 0.09-592 mu g l(-1) for EC and 32-242 mu g l(-1) and 30-277 mu g l(-1) As for LU, respectively. Detectable levels of MA(V) were reported in both provinces up to a concentration of 79 mu g l(-1) (equating to up to 33% of the total arsenic). Previously published literature has focused primarily on the inorganic arsenic species, however this study highlights the potentially significant concentrations of organoarsenicals present in natural waters.The potential for separating and preserving individual arsenic species in the field to avoid transformation during transport to the laboratory, enablng an accurate assessment of in situ arsenic speciation in water supplies is discussed.

Total arsenic and four arsenic species; arsenite (iAs(III)), arsenate (iAs(V)), dimethylarsinic acid (DMA(V)) and monomethylarsonic acid (MA(V)), are reported in 28 geothermal features from the Taupo Volcanic Zone (TVZ) and Waikato region of New Zealand. Samples were collected for arsenic speciation analysis via a solid phase extraction (SPE) kit allowing the separation, stabilisation and pre-concentration of the species at the time of sample collection in the field. This is the first research to present data for arsenic species collected by this technique in geothermal waters from New Zealand. Total arsenic concentrations, determined by inductively coupled plasma mass spectrometry (ICP-MS), ranged from 0.008 to 9.08 mg l(-1) As. The highest levels were discovered in three features in Tokaanu (Taumatapuhipuhi, Takarea #5 and #6), with arsenic concentrations of 8.59, 8.70 and 9.08 mg l(-1) As, respectively. Inorganic arsenic species were predominant in the geothermal waters, with arsenite contributing to more than 70% of the total arsenic in the majority of samples. Organic species were also determined in all samples, indicating the presence of microbial activity. A potential risk to human health was highlighted due to the high levels of arsenic, mainly as arsenite, in geothermal features linked to bathing pools. Further research is needed into dermal absorption as a potential route of arsenic exposure whilst bathing in these hot pools, as it may contribute to an occurrence of acute arsenic-related health problems.

Gunshot Residue (GSR) is residual material from the discharge of a firearm, which frequently provides crucial information in criminal investigations. Changes in ammunition manufacturing are gradually phasing out the heavy metals on which current forensic GSR analysis is based, and the latest Heavy Metal Free (HMF) primers urgently demand new forensic solutions. Proton scanning microbeam Ion Beam Analysis (IBA), in conjunction with the Scanning Electron Microscope equipped with an Energy Dispersive X-ray Spectrometer (SEM-EDS), can be introduced into forensic analysis to solve both new and old problems, with a procedure entirely commensurate with current forensic practice. Six cartridges producing GSR particles known to be interesting in casework by both experience and the literature were selected for this study. A standard procedure to relocate the same particles previously analysed by SEM-EDS, based on both secondary electron (SE) and X-ray imaging was developed and tested. Elemental Particle Induced X-ray Emission (PIXE) mapping of the emitted X-rays allowed relocation in a scan of 10μm×10μm of even a 1μm GSR particle. The comparison between spectra from the same particle obtained by SEM-EDS and IBA-PIXE showed that the latter is much more sensitive at mid-high energies. Results that are very interesting in a forensic context were obtained with particles from a cartridge containing mercury fulminate in the primer. Particle-induced gamma-ray emission (PIGE) maps of a particles from HMF cartridges allowed identification of Boron and Sodium in particles from hands using the B(p,αγ)Be, B(p,pγ)B and Na(p,pγ)Na reactions, which is extraordinary in a forensic context. The capability for quantitative analysis of elements within individual particles by IBA was also demonstrated, giving the opportunity to begin a new chapter in the research on GSR particles. The integrated procedure that was developed, which makes use of all the IBA signals, has unprecedented characterisation and discrimination power for GSR samples. © 2013 Elsevier Ireland Ltd.

The simple and effective approach of “dipping and drying” cotton yarn in a dispersion of poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) and multi-walled carbon nanotubes (MWCNT) resulted in the development of a highly conductive and flexible cotton fibres. Subsequent polyaniline (PANi) deposition yielded electrodes with significant biocompatible and antibacterial properties that could be fabricated (alongside quasi-reference electrodes) into solid-state wearable pH sensors, which achieve rapid, selective, and Nernstian responses (-61 ± 2 mV pH-1) over a wide pH range (2.0 – 12.0), even in a pH-adjusted artificial sweat matrix. This development represents an important progression towards the realisation of real-time, on-body, wearable sensors.

Objective: Very little is known about the relationship between postnatal methylmercury concentrations (via toenails as bioindicator) and behavioural characteristics of Pacific Island children living in New Zealand. The aim of this study was to explore the association between total mercury exposure and different domains of behavioural problems in Pacific children. Materials and Methods: A sample of nine-year-old Pacific Island children resident in Auckland, New Zealand participated in this study. Total mercury was determined in biological samples (toenail clippings) on behavioural problems as identified by mothers (using the child behaviour checklist). Specific behavioural domains, particularly aggression, rule breaking, attention and social problems were studied in relation to mercury exposure using toenails. The determination of mercury concentration in toenail clippings, after acid digestion was carried out using inductively coupled plasma mass spectrometry. Results: The observational study was conducted between July 2010 and July 2011 in which 278 eligible nine-year-old Pacific Island children were enrolled (Girls n= 58%; boys n=42%). Findings showed that 21% of the children had total toenail mercury concentrations (1.5 µg/g to 6 µg/g) higher than the United State Environmental Protection Agency recommended levels (RfD; 1 µg/g Hg) for optimal health in children. Aggressive behaviour was associated with total toenail mercury exposure after adjusting for gender, ethnicity and income levels (OR: 2.15 95% CI 1.45, 3.18 p-value< 0.05; OR 1.38 95% CI 0.83, 1.2 p value

A field method is reported for the speciation of arsenic in water samples that is simple, rapid, safe to use beyond laboratory environments, and cost effective. The method utilises solid-phase extraction cartridges (SPE) in series for selective retention of arsenic species, followed by elution and measurement of eluted fractions by inductively coupled plasma mass spectrometry (ICP-MS) for "total" arsenic. The method is suitable for on-site separation and preservation of arsenic species from water. Mean percentage accuracies (n = 25) for synthetic solutions of arsenite (As-III), arsenate (As-V), monomethylarsonic acid (MA), and dimethylarsinic acid (DMA) containing 10 mu g l(-1) As, were 98, 101, 94, and 105%, respectively. Data are presented to demonstrate the effect of pH and competing anions on the retention of the arsenic species. The cartridges were tested in the UK and Argentina at sites where arsenic was known to be present in surface and groundwaters, respectively, at elevated concentrations and under challenging matrix conditions. In Argentinean groundwater, 4-20% of speciated arsenic was present as MA and 20-73% as As-III. In UK surface waters, speciated arsenic was measured as 7-49% MA and 12-42% DMA. Comparative data from the field method using SPE cartridges and the laboratory method using liquid chromatography coupled to ICP-MS for all water samples provided a correlation of greater than 0.999 for As-III and DMA, 0.991 for MA, and 0.982 for As-V (P < 0.01).

Gene therapy for hemophilia A would be facilitated by development of smaller expression cassettes encoding factor VIII (FVIII), which demonstrate improved biosynthesis and/or enhanced biologic properties. B domain deleted (BDD) FVIII retains full procoagulant function and is expressed at higher levels than wild-type FVIII. However, a partial BDD FVIII, leaving an N-terminal 226 amino acid stretch (N6), increases in vitro secretion of FVIII tenfold compared with BDD-FVIII. In this study, we tested various BDD constructs in the context of either wild-type or codon-optimized cDNA sequences expressed under control of the strong, ubiquitous Spleen Focus Forming Virus promoter within a self-inactivating HIV-based lentiviral vector. Transduced 293T cells in vitro demonstrated detectable FVIII activity. Hemophilic mice treated with lentiviral vectors showed expression of FVIII activity and phenotypic correction sustained over 250 days. Importantly, codon-optimized constructs achieved an unprecedented 29- to 44-fold increase in expression, yielding more than 200% normal human FVIII levels. Addition of B domain sequences to BDD-FVIII did not significantly increase in vivo expression. These significant findings demonstrate that shorter FVIII constructs that can be more easily accommodated in viral vectors can result in increased therapeutic efficacy and may deliver effective gene therapy for hemophilia A.

High levels of vanadium have been reported in groundwater (< 0.05 – 5300 g L-1 V) from different parts of Argentina, yet no detailed study of vanadium speciation has been performed. A highly selective strong anion exchange – solid phase extraction (SAX-SPE) method was used (in-situ) for vanadium speciation analysis of groundwater samples from La Pampa - LP (General San Martin and Eduardo Castex) and Buenos Aires - BA (San German) provinces in Argentina. In this method both vanadyl (VIV) and vanadate (VV) were trapped by the complexation with disodium ethylenediaminetetraacetic acid on a pre-conditioned SAX cartridge. In the laboratory, vanadium species were separated at different eluent pH levels. VIV was eluted at pH 4 using methanol and tetrabutylammonium hydroxide. VV was eluted at pH 8 using dihydrogen ammonium phosphate. The eluted species were analysed by inductively coupled plasma mass spectrometry (ICP-MS). This method was validated using an inter-analytical method comparison with HPLC-ICP-MS. A Paired t-test revealed that there was no significant difference (probability, P < 0.05) between the two methods. VV was found to be predominate species in both sample collection areas (LP: 69 – 100%, BA: ‎33 – 89 % of species) over the range of 158.0 – 4748.0 g L-1 in LP and 88.5 – 504.0 g L-1 in BA. VIV was found at higher levels (29.0 - 301.0 g L-1) in Buenos Aires compared to General San Martin groundwater (4.4 – 161.0 g L-1). The results enhance the potential knowledge of the speciation of vanadium in terms of water quality and human health.

The use of unconventional biological materials in human trace element studies has increased in terms of published research studies. The aim of present study was to develop and validate the use of teardrop fluid for determining trace element levels in the human body. No study has been published in this area yet. This is a new non-invasive approach in the possible early diagnosis of the pathogenesis of type 2 diabetes. Human teardrop fluid samples were obtained from Karbala (Iraq) (n = 111) healthy individuals and with type 2 diabetes (n = 44); and London (UK) healthy individuals (n = 18). The levels of V, Cr, Mn, Fe, Cu, Zn, As, Sr and Cd were determined using an inductively coupled plasma mass equipped with collision cell technology for polyatomic ion correction (ICP-MS). Discriminate function analysis (DFA) was carried out to determine the set of variables that discriminated between the trace elements in teardrop fluid samples from healthy individuals and diabetic patients. The trace element levels of human teardrop fluid are similar for many elements to that reported for human blood serum in the literature. This is interesting since they have different physiological functions, although overall they are mainly water containing electrolytes (∼ 90 %) and solids (antibodies, hormones, etc). In general, for the study groups in Karbala, Iraq, significantly higher teardrop fluid levels of Mn and Sr were found in type 2 diabetic patients when compared with healthy individuals (evaluated using an F-test and a two-tailed t-test). The levels of V, Cu and As were found to be significantly higher (P  0.05). Cr and Cd were found to have similar levels for both study groups. Significantly higher teardrop fluid levels of V, Cr, Mn, Fe, Zn, As and Sr were found in healthy individuals from Karbala (Iraq) when compared with those from London (UK). In contrast, the levels of Cd observed to be significantly higher in London (UK) than Karbala. No statistical difference was found for Cu between the two healthy groups. Discriminate analysis showed that human teardrop fluid V, Mn, Zn, As, Sr and Cd levels could be used to discriminate between healthy and type 2 diabetes study groups in Karbala, Iraq (83 % of cases correctly classified). The use of human teardrop fluid for determining the trace element levels of human health conditions has been evaluated. Trace elemental levels are like that for blood serum which is widely used as an invasive method for assessing human health conditions. Sample collection for teardrop fluid is non-invasive and the application has potential for determining the trace element levels in healthy individuals and disorder conditions (like type 2 diabetes) in countries where cultural and gender sensitivity are issues with respect to the collection methods used for other body fluid samples.