Application of atomic absorption and plasma emission spectrometry for environmental analysis

The application of flame atomic absorption (FAAS), electrotehrmal atomic absorption (ETAAS), inductively coupled plasma emission (ICP), and direct-current plasma emission spectrometry (DCP) for the determination of major, minor, and trace elements in Urban Particulates (SRM 1648), Wear Metals in Oil (SRM 1084 and 1085), and Simulated Solid-Waste Leachates is described. Interference were encountered in the determination of the trace elements in SRM 1648 by ETAAS; however, these interferences were alleviated using a 1% solution of ammonium dibasic phosphate as a matrix modifier. The concentration of elements in SRM 1084 and 1085 and the simulated solid-waste leachates were significantly above the detection limits by FAAS or ICP and no analytical difficulty was encountered.     

Element mobility during metasomatism of granitic rocks in the Saint-Chély d'Apcher area (Lozère,France)

This paper summarises the behaviour of major and trace elements during hydrothermal alteration processes in the Vareilles albite deposit, Saint-Chély d' Apcher area (Lozère, France). Sampling focused mainly on fine- to medium-grained two-mica granite facies surrounding albitite veins in two open pits. The primary chemical variability inherent in sampling parent rock and analytical uncertainties can seriously affect element mobility calculations. Here we present a simple model that allows to discriminate between magmatic and alteration effects and to make a proper evaluation of the chemical changes that have caused the alteration. For this reason, a range of unaltered granites and albitites were sampled to evaluate the degree of parent rock heterogeneity. Duplicate measurements were performed by epithermal neutron activation analysis (ENAA) to obtain a reliable mean concentration for trace elements and to evaluate results reproducibility. ENAA measurements are completed by analysis of major elements by inductively coupled plasma-mass spectrometry (ICP-MS). The enrichment or depletion of an element during alteration, relative to its concentration in fresh parent rock, can be calculated on the basis of the assumed immobility of some elements during the process. In this study, we have assumed Ta as immobile element on the basis for his inert behaviour. The distinct differences in chemical change between altered and unaltered granite suggest the need to consider alteration event as an important parameter in evaluating granitic rocks for nuclear waste disposal.     

Intra-urban biomonitoring: Source apportionment using tree barks to identify air pollution sources

It is of great interest to evaluate if there is a relationship between possible sources and trace elements using biomonitoring techniques. In this study, tree bark samples of 171 trees were collected using a biomonitoring technique in the inner city of São Paulo. The trace elements (Al, Ba, Ca, Cl, Cu, Fe, K, Mg, Mn, Na, P, Rb, S, Sr and Zn) were determined by the energy dispersive X-ray fluorescence (EDXRF) spectrometry. The Principal Component Analysis (PCA) was applied to identify the plausible sources associated with tree bark measurements. The greatest source was vehicle-induced non-tailpipe emissions derived mainly from brakes and tires wear-out and road dust resuspension (characterized with Al, Ba, Cu, Fe, Mn and Zn), which was explained by 27.1% of the variance, followed by cement (14.8%), sea salt (11.6%) and biomass burning (10%), and fossil fuel combustion (9.8%). We also verified that the elements related to vehicular emission showed different concentrations at different sites of the same street, which might be helpful for a new street classification according to the emission source. The spatial distribution maps of element concentrations were obtained to evaluate the different levels of pollution in streets and avenues. Results indicated that biomonitoring techniques using tree bark can be applied to evaluate dispersion of air pollution and provide reliable data for the further epidemiological studies.     

长江、赣江鲢幼鱼耳石核区元素指纹特征分析及其在群体识别中的应用研究

采用激光剥蚀电感耦合等离子质谱分析技术（LA-ICP-MS）对2012、2014及2016年采自长江、赣江的鲢幼鱼耳石核区微量元素（Sr、Ba、Mg、Na、Si、Cr、Mn、Ca、Zn）进行了测定分析。结果显示:长江、赣江鲢幼鱼耳石核区4种微量元素与钙元素的比值（Sr∶Ca、Ba∶Ca、Si∶Ca、Mg∶Ca）在同一水体年际间基本不变,但不同水体（长江、赣江）鲢幼鱼群体间存在显著性差异,其中,Si∶Ca和Sr∶Ca比值对群体识别的贡献率最大。应用这4种元素比值的线性判别分析（LDFA）对长江鲢幼鱼群体整体判别成功率为92.11%,其中对2012年、2014年、2016年样本的判别成功率分别为：92.31%、93.33%、90.91%;对赣江鲢幼鱼群体整体判别成功率为92.31%,其中对2012、2014、2016年样本的判别成功率分别为：80.00%、96.77%、93.75%。研究表明,这4种元素比值可以作为识别长江和赣江鲢群体的环境元素指纹,LA-ICP-MS耳石元素指纹分析技术用于识别长江、赣江鲢群体确实有效可行。     

Trace element concentrations in tree rings as indicators of environmental pollution

Proton induced X-ray emission spectroscopy has been successfully used to measure variations in relative and absolute trace element concentration levels in tree rings. Valuable information on past concentration levels, stored in the tree rings have been obtained. Peaks associated with 15 elements have been identified in all X-ray spectra. Variations of trace elements levels in the tree rings reflect the variations in their availability from the environment.     

Trace determination of caffeine in surface water samples by liquid chromatography--atmospheric pressure chemical ionization--mass spectrometry (LC-APCI-MS)

A new method based on liquid-liquid extraction (LLE) coupled to reverse phase liquid chromatography and atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) has been applied to determine trace amounts of caffeine (1,3,7-trimethylxanthine) in surface water samples from a near coastal ecosystem such as Biscayne Bay, Florida. The rational behind the development of such method will be to evaluate the use of unmetabolized caffeine as a potential dissolved phase tracer of human waste contamination. The method allows for the determination of caffeine at levels as low as 4.0 ng/l (ppt) in both salt and freshwater by extracting and concentrating a 1-1 water sample to a final volume of 500 microl and using HPLC separation coupled to an atmospheric pressure chemical ionization mass spectrometry (APCI-MS) system operated in selected ion monitoring (SIM) for the protonated molecular ions (M + H(+)). Samples from different portions of Biscayne Bay and the Miami River, one of its major tributaries, were analyzed and caffeine was detected in those areas previously identified for consistently exceeding the water quality criteria for fecal coliform bacteria contamination. The caffeine concentration in the samples with positive detection was generally low at levels equal or lower than 41 ng/l. However, there is a marked difference between samples collected in open bay areas and those collected from the Miami River.     

Metals in the shell of Bathymodiolus azoricus from a hydrothermal vent site on the Mid-Atlantic Ridge

Specimens of the mussel Bathymodiolus azoricus were collected from Menez Gwen, a relatively shallow (850 m) hydrothermal vent field on the Mid-Atlantic Ridge. Each bivalve shell (n = 21) was individually cleaned by selective chemical. The residual crystal matrix of each shell was individually analysed for the concentrations of the minor elements magnesium and strontium and the trace elements iron, manganese, copper and zinc. The chemical composition of the crystal matrix is unusual. B. azoricus is identified as a species having one of the most strontium impoverished shells amongst the marine molluscs. For a bimineral species the magnesium concentration is also extraordinary low. Despite originating from a trace metal rich environment; the metal concentrations in the shells were exceptionally low. Mean concentrations of iron, manganese, copper and zinc were 20.6, 3.7, 0.6 and 9.4 microg g(-1) respectively. Minor and trace element concentrations exhibited a marked intra-population variability. Copper concentrations increased and iron and zinc concentrations decreased with increasing shell weight. Due to its insensitivity to the high environmental levels of trace elements and the variability in intra-population concentrations induced by shell weight the crystal matrix of the shell of B. azoricus has little potential for use in environmental trace metal monitoring in areas contiguous to deep-sea hydrothermal vents.     

The development of reference materials for acid rain research

The Center for Analytical Chemistry of the National Bureau of Standards is actively engaged in research to provide the basis for quality assurance in chemical measurements of rain water. Several types of SRMs are currently available which have direct applicability to atmospheric deposition programs. In addition, research is proceeding to develope and SRM specifically for rain-water analyses. Initial attempts, using a single solution containing all the components of rain and stored in glass ampoules, were unsuccessful due to the chemical instability of the solution. Current efforts are directed to improving the stability by using polyethylene bottles to store the solutions, and by preparing two separate solutions, one for the major components of rain (sulfate, nitrate, chloride, sodium, potassium, calcium, magnesium, ammonium, and hydrogen ions), and the other for the trace metals. Preliminary results on the stability of a pilot set of simulated rainwater solutions are encouraging.     

Dioxins and PCBs in game animals: Interspecies comparison and related consumer exposure

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (DL-PCB) and non-dioxin-like polychlorinated biphenyls (NDL-PCB) are ubiquitous, persistent toxic compounds that are highly bioaccumulative in nature. Wild-living animals are vulnerable to the negative impacts of human activity. Dioxins and PCBs enter the animal organisms through foraging. Due to the toxicological threat, much attention is paid to these compounds worldwide. The aim of this study was to determine the dioxin contamination status of three game animal species (red deer, roe deer, and wild boar) and compare the PCDD/F and PCB congener bioaccumulation in the muscles, abdominal fat and liver. The chemical analysis was performed by the isotope dilution technique (IDMS) with high-resolution gas chromatography coupled with high-resolution mass spectrometry (HRGC/HRMS). Dioxins and PCBs were found in specimens collected from all studied species, suggesting the presence of the test compounds in the environment of the animals. The highest concentrations were found in the livers of all animals. The toxic equivalent (TEQ) levels in the muscles, adipose tissue and liver were in the order red deer > roe deer > wild boar. PCDD/Fs were the dominant congeners in TEQ value. For all tested species, the dominant contributors to the total WHO-TEQ were PCB-126, 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDD. Among the PCDD/F congeners in the deer tissues, OCDD, OCDF and 2,3,4,7,8-PeCDF were dominant, while in wild boar, OCDD, 1,2,3,4,6,7,8-HpCDD and 1,2,3,4,6,7,8-HpCF occurred in the highest amounts. Among PCBs, PCB-105, 118, 156, 138, 153 and 180 were dominant in all species, but with different levels. The regular consumption of muscle meat from game animals should not cause unacceptable dioxin intake above the Tolerable Weekly Intake (TWI) value for children and adults. However, liver consumption should be avoided, especially by children and pregnant or lactating women. High consumption of contaminated liver may cause dioxin intake at levels up to 300% of TWI for adults and up to 700% TWI for children.     

Multi-elemental EDXRF mapping of polluted soil from former horticultural land

The distribution of major and trace elements was systematically investigated by use of energy dispersive X-ray fluorescence spectrometry (EDXRF) on a former horticultural soil. The purpose of the study was to combine mapping of soil element concentration levels with multivariate statistics for characterisation of soil metal pollution in relation to previous and present land use. A 1-ha study site was chosen from a former horticulture where a previous preliminary survey indicated increased concentration levels of toxic elements. The soil was sampled from the top 20 cm of the soil surface in a 10 x 10-m grid-like pattern covering the 1-ha study area. In addition, three soil profiles were studied. The elemental composition of the soil samples was investigated by EDXRF while the composition of aqueous soil extracts was determined by total reflection X-ray fluorescence spectrometry (TXRF). Based on mapping and multivariate statistically analysis of the data obtained by EDXRF, most elements were found in almost constant concentration levels in the top soil throughout the investigated site. However, the contents of the toxic elements Zn, Cu, As, and Pb were found to vary significantly within the area. Hence, the samples with high accumulations of As also contained relatively high amounts of Zn, Cu, and Pb, which indicates that toxic-element-containing pesticides have been applied to the soil surface in the area of the former green houses at the study site. The Pb/As mass ratio in the soil indicates that PbHAsO3 was the preferential lead arsenate used for pest management at the investigated site, while Cu as Bordeaux liquid (CuSO4) and Zn were applied to minimize the leaf damaging effect from the former compounds. Calculations indicated that As annually was applied to the soil in the former greenhouses in doses up to 4 kg As/ha while Pb had been annually applied in doses up to 12 kg Pb/ha. The enrichment of Zn, Cu, As and Pb was greatest in the top 20 cm of the soil and no anthropogenic enrichment of these elements occurred below a depth of 50 cm, indicating that the toxic elements are rather immobile in this soil. The results of this investigation suggest that EDXRF used in combination with multivariate statistics is a strong tool for multi-element mapping of elemental contents, sources and mobility in the terrestrial environment.     

Radioactivity and heavy metal composition of Nigerian phosphate rocks: possible environmental implications

Phosphate rock samples collected from the Dange Formation within the Sokoto basin were analyzed for trace element constituents using instrumental neutron activation analysis (INAA) and X-ray fluorescence analysis (XRFA) techniques, while natural activity concentrations due to 235U, 232Th, and 40K were determined by gamma-ray spectrometry. The analytical results show that the average concentrations of some toxic elements (As, Sb, Cr, and Zn) in phosphate rocks are not appreciably different from that in agricultural soils. However the U and Th contents are enriched significantly in comparison. The results were used to assess the environmental toxicity of heavy metals and radiation hazard attributable to the direct application of phosphate rock as fertilizer.     

Trends in the dissolution of metals from sediments collected during the Umitaka-Maru cruises using the microwave-acid digestion technique

Sediment samples were collected during the research vessel Umitaka-Maru cruises in the Gulf region from 15–16 December 1993 and 15–27 December 1994, from 19 and 24 locations, respectively. These samples were subjected to trace metal analysis to determine the 1991 Gulf War oil spill environmental impact in the area. The samples investigated are texturally classified into two main sediment classes: sand and mud. The total concentrations of lead, nickel, and vanadium found in the sediments from individual stations were investigated. The differences in trace metal concentrations reflect the variation in the overall composition of their host sediments. To better appraise the trace element composition of their host sediments and to determine the factors governing the trace metal distribution, the data were sub-divided into five groups among 1993 collections and seven groups during 1994. The concentration ranges of all three metals, lead (0.2–4.85), nickel (4.90–86.00), and vanadium (2.00–38.00) varied in different stations among the groups. The partitioning of trace elements between the detrial and non-detrital fractions of the sediments shows that: 1) The high concentrations of elements in mud is coupled with the increase in the detrital fraction; 2) In muddy sand sediments, nickel is bonded to the structural lattice of detrital minerals, whereas vanadium and lead held in the environmentally mobile fraction; and, 3) In sandy mud sediments, Ni is found in the detrital fraction, whereas V to slightly less extent and Pb show their non-detrital nature. The data were compared with unpolluted sediments throughout the ROPME Sea and worldwide, so the effect of anthropogenic enrichment upon the absolute concentration of the elements is minimal.     

Source apportionment of fine carbonaceous particles by positive matrix factorization at Gosan background site in East Asia

Fine particle (aerodynamic diameter <2.5 microm) samples were collected during six intensive measurement periods from November 2001 to August 2003 at Gosan, Jeju Island, Korea, which is one of the representative background sites in East Asia. Chemical composition of these aerosol samples including major ion components, trace elements, organic and elemental carbon (OC and EC), and particulate polycyclic aromatic hydrocarbons (PAHs) were analyzed to study the impact of long-range transport of anthropogenic aerosol. Aerosol chemical composition data were then analyzed using the positive matrix factorization (PMF) technique in order to identify the possible sources and estimate their contribution to particulate matter mass. Fourteen sources were then resolved including soil dust, fresh sea salt, transformed natural source, ammonium sulfate, ammonium nitrate, secondary organic carbon, diesel vehicle, gasoline vehicle, fuel oil combustion, biomass burning, coal combustion, municipal incineration, metallurgical emission source, and volcanic emission. The PMF analysis results of source contributions showed that the natural sources including soil dust, fresh and aged sea salt, and volcanic emission contributed to about 20% of the measured PM(2.5) mass. Other primary anthropogenic sources such as diesel and gasoline vehicle, coal and fuel oil combustion, biomass burning, municipal incineration, metallurgical source contributed about 34% of PM(2.5) mass. Especially, the secondary aerosol mainly involved with sulfate, nitrate, ammonium, and organic carbon contributed to about 39% of the PM(2.5) mass.     

Separation and measurement of thorium, plutonium, americium, uranium and strontium in environmental matrices

A technique for the isolation of thorium (Th), plutonium (Pu), americium (Am), uranium (U) and strontium (Sr) isotopes from various environmental matrices has been adapted from a previously published method specific to water samples (Maxwell, 2006). Separation and isolation of the various elemental fractions from a single sub-sample is possible, thereby eliminating the need for multiple analyses.The technique involves sample dissolution, concentration via calcium phosphate co-precipitation, rapid column extraction using TEVA™, TRU™ and Sr-Spec™ resin cartridges, alpha spectrometry for Th, Pu, U and Am and Cerenkov counting for Sr.Various standard reference materials were analysed and chemical yields are in the range of 70-80% for Th, Am, U and Sr and 50-60% for Pu. Sample sizes of up to 10 L for water, 5 g for dry soil and sediment and 10 g for dry vegetation and seaweed can be processed using this technique.     

Ultraviolet irradiation of municipal wastewater: Evaluation of effects on organic constituents

A comparison of chromatograms derived from the UV-absorbing and oxidizable constituents present in primary and secondary municipal wastewater effluents indicates that exposure to UV irradiation at disinfection levels results in only slight chemical changes. The most pronounced chemical effects to nonvolatile organic constituents in wastewater effluents have been observed at irradiation levels in excess of those necessary for disinfection. Aliquots of effluents before and after exposure to varying levels of UV irradiation were concentrated by lyophilization prior to liquid chromatographic (LC) analysis. Anion-exchange chromatographic techniques utilizing a modified ultraviolet detector coupled in series with a cerate oxidative monitor provided excellent resolution and sensitivity in the determination of chemical changes occurring in the effluents as a result of exposure to different irradiation levels. The total coliform counts for each irradiated effluent were determined by the membrane-filter technique to evaluate the effectiveness of UV irradiation as a disinfection process for municipal wastewaters. Changes in biochemical oxygen demand (BOD), chemical oxygen demand (COD), total organic carbon (TOC), and total Kjeldahl nitrogen (TKN) at different levels of exposure to UV irradiation are presented. The results of these determinations and the gas chromatography/mass spectrometry data characterizing the observed chemical changes are discussed.     

Wet and dry deposition of 129I in Seville (Spain) measured by accelerator mass spectrometry.

Iodine-129 (T1/2 = 1.57 x 10(7) yr) concentrations have been determined by accelerator mass spectrometry in rainwater samples taken at Seville (southwestern Spain) in 1996 and 1997. This technique allows a reduction in the detection limits for this radionuclide in comparison to radiometric counting and other mass spectrometric methods such as ICP-MS. Typical 129I concentrations range from 4.7 x 10(7) 129I atoms/l (19.2%) to 4.97 x 10(9) 129I atoms/l (5.9%), while 129I depositions are normally in the order of 10(8)-10(10) atoms/m2d. These values agree well with other results obtained for recent rainwater samples collected in Europe. Apart from these, the relationship between 129I deposition and some atmospheric factors has been analyzed, showing the importance of the precipitation rate and the concentration of suspended matter in it.     

Trace element pollution records in some UK lake sediments, their history, influence factors and regional differences

Sediment cores were taken from six sites across the UK. Apart from Banbury Reservoir in London, all the other sites are relatively remote lakes. Trace elements Pb, Zn, Cu, Cd, Cr, Ni, Sn, As and V, major elements such as Fe, Mn, Ti and Al were analysed, and organic content measured as loss-on-ignition was determined in all of these cores. The result shows that these relatively remote sites have experienced enhanced atmospheric deposition of anthropogenically derived trace elements for over 100 years, and the contamination might start before industrialisation. Trace metal contamination remains the highest level at Banbury Reservoir showing "pollution source" influence. Despite the considerable reduction in atmospheric deposition in recent years, although some of the element concentrations in the surface sediments have declined, they are still much higher than their natural background values. In these sites, trace element pollution records have been influenced by many different factors. Redox condition could affect As distribution in the sediments. Sediment matrix could also affect trace element pollution signal. Apart from direct atmospheric deposition, the distributions of trace elements in the sediments have been affected by forestry activities and catchment erosion, and more contaminated soil in-wash could increase sediment pollution whilst less contaminated soil could dilute sediment pollution. In some sites, data suggest that catchment in-wash is an important source of elements for the lakes.     

Minor and trace elements in the shell of Patella aspera (Röding 1798)

Specimens of the limpet Patella aspera were collected from a clean, coastal marine site and a contaminated estuary on the south coast of Portugal. The shells were analysed individually for their minor (Mg, Sr) and trace element (Fe, Mn, Zn) content. Mean concentrations of these elements in the shell of P. aspera were 4651, 1318, 35.8, 29.9 and 5.5 microg g(-1), respectively. The elemental concentrations exhibited both a marked intra- and inter-population variability. Despite the variability within individual populations, significant differences in the trace element composition were apparent between the shells taken from the two sites. Small shells (< 2 g) provided the best resolution between sites for both manganese and iron. Differences in zinc were best resolved for larger shells. The shell of P. aspera has an extraordinarily high magnesium concentration, which is insensitive to gross salinity differences, and a trace metal assemblage that can be interpreted in terms of environmental exposure. On these grounds, it is recommended that the shell of P. aspera is a tissue for potential use in environmental trace metal monitoring.     

Geochemical features of soil and plant cover in the zone of recent explosive volcanism

Geochemical specialization of the soil and plant cover has been revealed in the vicinity of the active Karymsky volcano (the eastern coast of the Kamchatka Peninsula), where the concentrations of most trace elements in the soil are lower than their clarkes but those in plants exceed their contents commonly recorded in living matter. Freshly deposited volcanic ash is enriched with movable forms of trace elements. As a result of hypergenic processes, they are dissolved and transferred to ground and surface waters, which accounts for a rich mineral composition of vegetation.     

Heavy metals in agricultural soils of the European Union with implications for food safety

Soil plays a central role in food safety as it determines the possible composition of food and feed at the root of the food chain. However, the quality of soil resources as defined by their potential impact on human health by propagation of harmful elements through the food chain has been poorly studied in Europe due to the lack of data of adequate detail and reliability. The European Union's first harmonized topsoil sampling and coherent analytical procedure produced trace element measurements from approximately 22,000 locations. This unique collection of information enables a reliable overview of the concentration of heavy metals, also referred to as metal(loid)s including As, Cd, Cr, Cu, Hg, Pb, Zn, Sb. Co, and Ni. In this article we propose that in some cases (e.g. Hg and Cd) the high concentrations of soil heavy metal attributed to human activity can be detected at a regional level. While the immense majority of European agricultural land can be considered adequately safe for food production, an estimated 6.24% or 137,000 km² needs local assessment and eventual remediation action.