Sequential Determination of Cd, Cu and Pb in Tea Leaves by Slurry Introduction to Thermospray Flame Furnace Atomic Absorption Spectrometry

A simple procedure for the sequential determination of Cd, Cu and Pb in tea leaves by slurry introduction to thermospray flame furnace atomic absorption spectrometry was developed. Detection limits were 0.05 mg kg-1 for Cd, 2.1 mg kg-1 for Cu and 0.68 mg kg-1 for Pb using 0.67 % (m/v) slurries (100 mg/15 mL). © 2013 Springer Science+Business Media New York.

Evaluation and Application of TS-FF-AAS System Using Ceramic Tube as Atomization Cell for Tin Determination in Canned Foods

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Sistema TS-FF-AAS com chama acetileno-ar como alternativa em relação à chama acetileno-óxido nitroso em FAAS na determinação de estanho

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Comparison of metallic and ceramic tubes as atomization cells for tin determination by TS-FF-AAS

This work describes the development of an analytical procedure for on-line tin determination using thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS). Two tubes were evaluated as atomization cells: a metallic tube (Ni-Cr, principal components composition: 73.95% Ni and 16.05% Cr) and a ceramic tube (99.8% Al2O3). The use of air as the carrier was made by employing a Rheodyne valve to inject the samples, allowing an analytical frequency of 90 h(-1) and avoiding sample dispersion. The carrier flow rate (air), sample volume injected, and acid concentration (HCl) were evaluated for the optimization of the TS-FF-AAS system. The sensitivity for 50 mL of analytical solution with TS-FF-AAS was 2 and 5 times higher (to metallic and ceramic tube, respectively) than using an acetylene-nitrous oxide flame with pneumatic aspiration (requiring a sample volume of approximately 20 times higher.

Avaliação da espectrometria de absorção atômica com nebulização térmica em tubo aquecido em chama (TS-FF-AAS) para determinação de Cd, Cu, Pb e Zn em álcool combustível e óleo diesel

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Peat as a natural solid-phase for copper preconcentration and determination in a multicommuted flow system coupled to flame atomic absorption spectrometry

The physical and chemical characteristics of peat were assessed through measurement of pH, percentage of organic matter, cationic exchange capacity (CEC), elemental analysis, infrared spectroscopy and quantitative analysis of metals by ICP OES. Despite the material showed to be very acid in view of the percentage of organic matter, its CEC was significant, showing potential for retention of metal ions. This characteristic was exploited by coupling a peat mini-column to a flow system based on the multicommutation approach for the in-line copper concentration prior to flame atomic absorption spectrometric determination. Cu(II) ions were adsorbed at pH 4.5 and eluted with 0.50 mol L(-1) HNO(3). The influence of chemical and hydrodynamic parameters, such as sample pH, buffer concentration, eluent type and concentration, sample flow-rate and preconcentration time were investigated. Under the optimized conditions, a linear response was observed between 16 and 100 mu g L(-1), with a detection limit estimated as 3 mu g L(-1) at the 99.7% confidence level and an enrichment factor of 16. The relative standard deviation was estimated as 3.3% (n = 20). The mini-column was used for at least 100 sampling cycles without significant variation in the analytical response. Recoveries from copper spiked to lake water or groundwater as well as concentrates used in hemodialysis were in the 97.3-111 % range. The results obtained for copper determination in these samples agreed with those achieved by graphite furnace atomic absorption spectrometry (GFAAS) at the 95% confidence level. (C) 2009 Elsevier B.V. All rights reserved.

Direct determination of iron in sand using solid sampling graphite furnace atomic absorption spectrometry

A fast and reliable method for the direct determination of iron in sand by solid sampling graphite furnace atomic absorption spectrometry was developed. A Zeeman-effect 3-field background corrector was used to decrease the sensitivity of spectrometer measurements. This strategy allowed working with up to 200 mu g of samples, thus improving the representativity. Using samples with small particle sizes (1-50 mu m) and adding 5 mu g Pd as chemical modifier, it was possible to obtain suitable calibration curves with aqueous reference solutions. The pyrolysis and atomization temperatures for the optimized heating program were 1400 and 2500 degrees C, respectively. The characteristic mass, based on integrated absorbance, was 56 pg, and the detection limits, calculated considering the variability of 20 consecutive measurements of platform inserted without sample was 32 pg. The accuracy of the procedure was checked with the analysis of two reference materials (IPT 62 and 63). The determined concentrations were in agreement with the recommended values (95% confidence level). Five sand samples were analyzed, and a good agreement (95% confidence level) was observed using the proposed method and conventional flame atomic absorption spectrometry. The relative standard deviations were lower than 25% (n = 5). The tube and boat platform lifetimes were around 1000 and 250 heating cycles, respectively.

Brominated flame retardants in the Australian population : 1993-2009

Brominated flame retardants, including hexabromocyclododecane (HBCD) and polybrominated diphenyl ethers (PBDEs) are used to reduce the flammability of a multitude of electrical and electronic products, textiles and foams. The use of selected PBDEs has ceased, however, use of decaBDE and HBCD continues. While elevated concentrations of PBDEs in humans have been observed in Australia, no data is available on other BFRs such as HBCD. This study aimed to provide background HBCD concentrations from a representative sample of the Australian population and to assess temporal trends of HBCD and compare with PBDE concentrations over a 16 year period. Samples of human milk collected in Australia from 1993 to 2009, primarily from primiparae mothers were combined into 12 pools from 1993 (2 pools); 2001; 2002/2003 (4 pools); 2003/2004; 2006; 2007/2008 (2 pools); and 2009. Concentrations of ∑HBCD ranged from not quantified (nq) to 19 ng g−1 lipid while α-HBCD and γ-HBCD ranged from nq to 10 ng g−1 lipid and nq to 9.2 ng g−1 lipid. β-HBCD was detected in only one sample at 3.6 ng g−1 lipid while ∑4PBDE ranged from 2.5 to 15.8 ng g−1 lipid. No temporal trend was apparent in HBCD concentrations in human milk collected in Australia from 1993 to 2009. In comparison, PBDE concentrations in human milk show a peak around 2002/03 (mean ∑4PBDEs = 9.6 ng g−1 lipid) and 2003/04 (12.4 ng g−1 lipid) followed by a decrease in 2007/08 (2.7 ng g−1 lipid) and 2009 (2.6 ng g−1 lipid). In human blood serum samples collected from the Australian population, PBDE concentrations did not vary greatly (p = 0.441) from 2002/03 to 2008/09. Continued monitoring including both human milk and serum for HBCD and PBDEs is required to observe trends in human body burden of HBCD and PBDEs body burden following changes to usage.

Human exposure to brominated flame retardants

Human polybrominated diphenyl ether (PBDE) exposure occurs through a range of pathways including: ingestion of dust including hand-to-mouth contact; inhalation (air/particulate matter); and ingestion via food including the unique nutrition sources of human milk and placental transfer. While inhalation has been deemed a minor source of exposure, ingestion of food and dust make greater contributions to overall PBDE body burden with intake via dust reported to be much higher in infants than in adults. PBDEs have been detected in samples of human milk, blood serum, cord blood, and adipose tissue worldwide. Concentrations have been found to be highest in populations from North America, followed by Australia, Europe, and Asia. While factors such as gender and parity may not affect concentrations, occupational exposure and age (infants and children) are associated with higher PBDE concentrations. In contrast to “traditional” persistent organic pollutants, there is an inverse relationship between PBDE body burden and age. Predicted body burden calculated using available information on intake and elimination rates of BFRs appears to underestimate measured human body burden data obtained through analysis of BFRs in blood or human milk. This may be due to unknown exposure or inaccurate elimination data. Further exposure studies should focus on younger age groups and an investigation of human PBDE half-lives.

Health consequences of exposure to brominated flame retardants : a systematic review

Background Brominated flame retardants (BFRs), are chemicals widely used in consumer products including electronics, vehicles, plastics and textiles to reduce flammability. Experimental animal studies have confirmed that these compounds may interfere with thyroid hormone homeostasis and neurodevelopment but to date health effects in humans have not been systematically examined. Objectives To conduct a systematic review of studies on the health impacts of exposure to BFRs in humans, with a particular focus on children. Methods A systematic review was conducted using the Medline and EMBASE electronic databases up to 1 February 2012. Published cohort, cross-sectional, and case-control studies exploring the relationship between BFR exposure and various health outcomes were included. Results In total, 36 epidemiological studies meeting the pre-determined inclusion criteria were included. Plausible outcomes associated with BFR exposure include diabetes, neurobehavioral and developmental disorders, cancer, reproductive health effects and alteration in thyroid function. Evidence for a causal relationship between exposure to BFRs and health outcomes was evaluated within the Bradford Hill framework. Conclusion Although there is suggestive evidence that exposure to BFRs is harmful to health, further epidemiological investigations particularly among children, and long-term monitoring and surveillance of chemical impacts on humans are required to confirm these relationships.

Assessment of the concentrations of polybrominated diphenyl ether flame retardants in the Australian population : levels in blood

Polybrominated diphenyl ethers (PBDEs), a common class of brominated flame retardants, are a ubiquitous part of our built environment, and for many years have contributed to improved public safety by reducing the flammability of everyday goods. Recently, PBDEs have come under increased international attention because of their potential to impact upon the environment and human health. Some PBDE compounds have been nominated for possible inclusion on the Stockholm Convention on Persistent Organic Pollutants, to which Australia is a Party. Work under the Stockholm Convention has demonstrated the capacity of some PBDEs to persist and accumulate in the environment and to be carried long distances. Much is unknown about the impact of PBDEs on living organisms, however recent studies show that some PBDEs can inhibit growth in colonies of plankton and algae and depress the reproduction of zooplankton. Laboratory mice and rats have also shown liver disturbances and damage to developing nervous systems as a result of exposure to PBDEs. In 2004, the Australian Government Department of the Environment and Water Resources began three studies to examine levels of PBDEs in aquatic sediments, indoor environments and human blood, as knowledge about PBDEs in Australia was very limited. The aim of these studies was to improve this knowledge base so that governments were in a better position to consider appropriate management actions. Due to the high costs for laboratory analysis of PBDEs, the number of samples collected for each study was limited and so caution is required when interpreting the findings. Nevertheless, these studies will provide governments with an indication of how prevalent PBDEs are in the Australian population and the environment and will also contribute to international knowledge about these chemicals. The Department of the Environment and Water Resources will be working closely with othergovernment agencies, industry and the community to investigate any further action that may be required to address PBDEs in Australia.

Wastewater analysis of Census day samples to investigate per capita input of organophosphorus flame retardants and plasticizers into wastewater

The use of organophosphate esters (PFRs) as flame retardants and plasticizers has increased due to the ban of some brominated flame retardants. There is however some concern regarding the toxicity, particularly carcinogenicity and neurotoxicity, of some of the PFRs. In this study we applied wastewater analysis to assess use of PFRs by the Australian population. Influent samples were collected from eleven wastewater treatment plants (STPs) in Australia on Census day and analysed for PFRs using gas chromatography coupled with mass spectrometry (GC-MS). Per capita mass loads of PFRs were calculated using the accurate Census head counts. The results indicate that tris(2-butoxyethyl) phosphate (TBOEP) has the highest per capita input into wastewater followed by tris(2-chloroisopropyl) phosphate (TCIPP), tris(isobutyl) phosphate (TIBP), tris(2-chloroethyl) phosphate (TCEP) and tris(1,3-dichloroisopropyl) phosphate (TDCIPP). Similar PFR profiles were observed across the Australian STPs and a comparison with European and U.S. STPs indicated similar PFR concentrations. We estimate that approximately 2.1 mg person−1 day−1 of PFRs are input into Australian wastewater which equates to 16 tonnes per annum.

Towards development of a rapid and effective non-destructive testing strategy to identify brominated flame retardants in the plastics of consumer products

Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants (BFRs) once extensively used in the plastics of a wide range of consumer products. The listing of certain congeners that are constituents of commercial PBDE mixtures (including c-octaBDE) in the Stockholm Convention and tightening regulation of many other BFRs in recent years have created the need for a rapid and effective method of identifying BFR-containing plastics. A three-tiered testing strategy comparing results from non-destructive testing (X-ray fluorescence (XRF)) (n = 1714), a surface wipe test (n = 137) and destructive chemical analysis (n = 48) was undertaken to systematically identify BFRs in a wide range of consumer products. XRF rapidly identified bromine in 92% of products later confirmed to contain BFRs. Surface wipes of products identified tetrabromobisphenol A (TBBPA), c-octaBDE congeners and BDE-209 with relatively high accuracy (> 75%) when confirmed by destructive chemical analysis. A relationship between the amounts of BFRs detected in surface wipes and subsequent destructive testing shows promise in predicting not only the types of BFRs present but also estimating the concentrations present. Information about the types of products that may contain persistent BFRs will assist regulators in implementing policies to further reduce the occurrence of these chemicals in consumer products.

In situ reaction furnace for real-time XRD studies

The new furnace at the Materials Characterization by X-ray Diffraction beamline at Elettra has been designed for powder diffraction measurements at high temperature (up to 1373 K at the present state). Around the measurement region the geometry of the radiative heating element assures a negligible temperature gradient along the capillary and can accommodate either powder samples in capillary or small flat samples. A double capillary holder allows flow-through of gas in the inner sample capillary while the outer one serves as the reaction chamber. The furnace is coupled to a translating curved imaging-plate detector, allowing the collection of diffraction patterns up to 2[theta] [asymptotically equal to] 130°.

CMC simulations of lifted turbulent jet flame in a vitiated coflow

Lifted turbulent jet diffusion flame is simulated using Conditional Moment Closure (CMC). Specifically, the burner configuration of Cabra et al. [R. Cabra, T. Myhrvold, J.Y. Chen. R.W. Dibble, A.N. Karpetis, R.S. Barlow, Proc. Combust. Inst. 29 (2002) 1881-1887] is chosen to investigate H-2/N-2 jet flame supported by a vitiated coflow of products of lean H-2/air combustion. A 2D, axisymmetric flow-model fully coupled with the scalar fields, is employed. A detailed chemical kinetic scheme is included, and first order CIVIC is applied. Simulations are carried out for different jet velocities and coflow temperatures (T-c) The predicted liftoff generally agrees with experimental data, as well as joint-PDF results. Profiles of mean scalar fluxes in the mixture fraction space, for T-c = 1025 and 1080 K reveal that (1) Inside the flame zone, the chemical term balances the molecular diffusion term, and hence the Structure is of a diffusion flamelet for both cases. (2) In the pre-flame zone, the structure depends on the coflow temperature: for the 1025 K case, the chemical term being small, the advective term balances the axial turbulent diffusion term. However, for the 1080 K case. the chemical term is large and balances the advective term, the axial turbulent diffusion term being small. It is concluded that, lift-off is controlled (a) by turbulent premixed flame propagation for low coflow temperature while (b) by autoignition for high coflow temperature. (C) 2009 The Combustion Institute. Published by Elsevier Inc. All rights reserved.