Analytical methods and validation for determining trace elements in red wines

The objective of this work is to quantify As, Hg, Cd, Ni and Pb in Portuguese red wines. First, the methods for the quantification of trace elements in red wines were validated. Several pre-treatments were compared, namely a pre-digestion process with HNO₃, a pre-oxidation step with H₂O₂, and a spiking step of wine samples with a known concentration of the trace elements analyzed. Except for As, it was determined that the quantification of the trace elements does not require a pre-digestion process with HNO₃. For all of the trace elements analyzed, a pre-oxidation step with H₂O₂ may enable an accurate quantification. The techniques chosen for the quantification of trace elements were hydride generation atomic absorption spectrometry (HGAAS) for As and Hg, electrothermal atomic absorption spectrometry (ETAAS) for Cd, and flame atomic absorption spectrometry (FAAS) for Ni and Pb. In the second stage of this work, 25 Portuguese red wines spanning all of the red wine-producing regions were analyzed for all of the five trace elements referred to above. Only Cd and Pb have shown concentrations above the limit values defined by the “Organization Internationale de la Vigne et du Vin.” The Target Hazard Quotient (THQ) equation was used to determine in which wine-producing regions that wine consumption can be a problem for public health in terms of the concentrations of the five trace elements analyzed. THQ values have indicated that for the universe of the 25 red wines analyzed no region produces wines that can pose problems for public health, when the Portuguese red wine standard consumption is considered.     

Evaluating the effect of age and area of residence in the metal and metalloid contents in human hair and urban topsoils

Monitoring the levels of trace elements in hair can allow estimating the effects of the geographical location and also can provide a notion of the metal body burden. However, the use of human hair is controversial due to the different confounding factors that could affect the presence of trace elements in hair. As a result, a comprehensive monitoring study was performed in Alcalá de Henares, one of the major cities in the Madrid region, Spain. Trace elements have been monitored in urban topsoils and in human hair of two well-defined and healthy groups of population: children (6–9 years) and adolescents (13–16 years). The city was divided into four areas or zones with different characteristics to assess the possible effect of area of residence and age in the presence of Al, As, Be, Cd, Cr, Cu, Hg, Mn, Pb, Sn, Ti, Tl and Zn in soils and hair. There is no current hypothesis that explains the possible effect of the area of monitoring in the distribution of Be, Cr, Ni, Sn and Ti found in these urban soils, maybe because urban soils receive high disturbance, and there are many factors involved. The presence of most of the trace elements monitored was significantly higher in the hair of the children population, except for Sn and Zn. This could be attributed mainly to dietary habits. Other factors influencing metal content in hair such as environmental factors would have had a minimal effect in the population groups here studied. Finally, none of the levels of trace elements studied in hair were significantly correlated with levels measured in the topsoils of public parks in Alcalá de Henares, with the exception of Pb in adolescent participants.     

The presence of vanadium in groundwater of southeastern extreme the pampean region Argentina Relationship with other chemical elements

Changes in the quality of groundwater resources are related to the presence and concentration of contaminants, especially trace elements such as arsenic, boron, fluoride and vanadium. Vanadium is a rare element naturally abundant, generally found in combination with other elements. Vanadium pentoxide is known to have aneugenic effects. Thus, a study was carried out to assess the presence of vanadium in the groundwater of the southeastern pampean region of Argentina, which constitutes the main water supply for the local population. Statistical and correlational analyses were applied to identify possible interrelationships between vanadium and another chemical elements. Vanadium was found in all groundwater samples. The minimum and maximum vanadium concentrations found were 0.05 mg/l and 2.47 mg/l, respectively. Vanadium is significantly correlated with other trace elements such as arsenic, fluoride and boron. The interrelationship between vanadium and the presence of volcanic glass in sediments is not significant as expected.     

Levels of metals, PCBs, PCNs and PAHs in soils of a highly industrialized chemical/petrochemical area: temporal trend

In 2005, the concentrations of various metals and organic pollutants were analyzed in soils collected in different areas of Tarragona (Catalonia, Spain), where an important chemical/petrochemical complex is located. The levels of seven elements (As, Cd, Cr, Hg, Mn, Pb and V), as well as those of polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs) and polycyclic aromatic hydrocarbons (PAHs) were determined in soils, and compared with those obtained in a background study carried out in 2002. Only Cd and Pb showed significant higher concentrations in the petrochemical zone, while no significant differences were found for the remaining elements. In turn, vanadium was the only element showing a significant increase in the concentration between 2002 and 2005. With regard to the organic pollutants, no significant differences were found according to the area of sampling. However, an increase in naphthalene levels was observed during the period 2002-2005 in soils of the chemical and petrochemical areas. According to the present results, it is suggested that the levels of vanadium must be periodically monitored to assure that the important industrialization of Tarragona does not mean health risks for the population living near the complex.     

Essential and non-essential element concentrations in two sleeper shark species collected in arctic waters

A number of elements/metals have increased in arctic biota and are of concern due to their potential toxicity. Most studies on elements in the Arctic have focused on marine mammals and seabirds, but concentrations in the Greenland shark (Somniosus microcephalus) and Pacific sleeper shark (Somniosus pacificus), the only two shark species known to regularly inhabit arctic waters, have never been reported. To address this data gap, concentrations and patterns of 25 elements were analyzed in liver of Greenland sharks collected about Cumberland Sound (n=24) and Pacific sleeper sharks collected about Prince William Sound (n=14). Several non-essential elements differed between species/locations, which could suggest geographical exposure differences or ecological (e.g., diet) differences between the species. Certain essential elements also differed between the two sleeper sharks, which may indicate different physiological requirements between these closely related shark species, although information on such relationships are lacking for sharks and fish.     

Relation between mortality of young walleye (Stizostedion vitreum) and recruitment with different forms of compensation

The relation between mortality of young fish and recruitment is important for assessment of the environmental effects of facilities that kill large numbers of young fish, such as electric power stations and hydropower plants. A simulation model with a bioenergetic growth component was applied to examine the relation between mortality of young and recruitment for walleye (Stizostedion vitreum) with different forms of population regulation, including: food limited growth, food limited growth with size-dependent mortality, and food limited growth with age at maturity dependent on size. With food limited growth small increases in mortality of young reduced recruitment considerably, but the population slowly approached a new equilibrium. If mortality of young increased when growth was food limited, the population approached a new equilibrium of natality and mortality because with fewer individuals there was more food per individual, and individuals were larger in size and produced more eggs; this feedback adjusted natality to equal mortality. With either mortality or age at maturity dependent on size, large increases in mortality of young resulted in only small decreases in recruitment.     

Forest fire emissions in Portugal: a contribution to global warming?

A forecast of expected evolution of carbon dioxide (CO(2)) emissions in Portugal between 1988 and 2010 is presented. Predictions show that CO(2) emissions will almost double in the next twenty years. The equivalent potential CO(2) emissions from nitrogen oxides (NO(x)) and volatile organic compounds (VOC), for a time horizon of 20 years, is also presented. NO(x) and VOC emissions seem to make a significant contribution to the global warming potential of Portuguese emissions. Estimates of CO(2) emissions due to forest fires have been made, oriented towards the study of the Portuguese contribution to the global warming. If the burned area exceeds 100 000 ha this contribution could reach 7% of the total Portuguese CO(2) emissions. The global warming potential of Portuguese forest emissions were also calculated. The climate change predicted to Portugal could be responsible for an increase in the forest fires and consequently for a greater contribution of its emissions to the total values. It was concluded that it is important to quantify emissions of the greenhouse gases, including the contribution of forest fire emissions, not only in Portugal, but in all the Southern European countries.     

Total element concentration and chemical fractionation in airborne particulate matter from Santiago,Chile

Total element determination and chemical fractionation were carried out in airborne particulate matter (PM₁₀) from the Cerrillos monitoring station in Santiago, Chile, sampled in July (winter), 1997–2003.Element concentration in the period under study (1997–2003) was statistically analyzed through cluster analysis in order to identify groups of elements having similar behavior along time. Elements such as Cd, Cu, Pb, Ni, As and Mg show a clear decrease in concentration with time. On the contrary, chromium increases its concentration almost linearly during the period.In order to estimate whether the presence of a certain element in PM₁₀ matrix is mainly due to anthropogenic or natural processes, the enrichment factor of each element was determined.According to their behavior in the sequential extraction procedure, the elements were grouped by multivariate analysis in three clusters: (a) those mobile elements (Pb, Cd, Zn, Mn, Cu and As) which are weakly bound to the matrix (fractions 1 and 2) (b) those elements (V, Ti, and Cr) mainly bound to carbonates and oxides (fraction 3) and (c) the most immobile elements (Ni, Mo, Ca, Mg, Ba and Al), mainly bound to silicates and organic matter (fraction 4). A source of great concern is the fact that elements of such high toxicity as Pb, Cd and As are highly concentrated in both mobile fractions, indicating that these elements have a direct impact on the environment and on the health of the exposed population.     

Concentration and Composition of Atmospheric Aerosols from the 1995 SEAVS Experiment and a Review of the Closure between Chemical and Gravimetric Measurements

ABSTRACT

We summarize the results from the various measurements and the inter-sampler comparisons from Southeastern Aerosol and Visibility Study (SEAVS), a study with one of its objectives to test for closure among chemical, gravimetric and optical measurements of atmospheric aerosol particles. Sulfate and organics are the dominant components of the SEAVS fine particles (nominally, particles with aerodynamic diameter <2.5 u,m) but between 28 and 42% (range over various samplers) of the gravimetrically measured total fine particle concentration is unidentified by the chemical measurements. Estimates of water associated with inorganic components and measurement imprecision do not totally explain the observed difference between gravimetric and chemical measurements. We examine the theoretical and empirical basis for assumptions commonly made in the published literature to extrapolate total fine particle concentration on the basis of chemical measurements of ions, carbon and elements.     

Associations of essential element serum concentrations with autism spectrum disorder

Environmental Science and Pollution Research - This case–control study explored the associations between autism spectrum disorder (ASD) and the serum concentration of nine chemical elements...     

Calibration and validation of a dynamic water model in agricultural scenarios

A dynamic aquatic model (DynA model) was previously developed to predict the fate of a chemical in aquatic scenarios characterized by daily or periodic changes in several input parameters. DynA model is here calibrated with data obtained from the literature in specific unsteady state scenarios, such as those of rice fields. The results obtained for two herbicides (cinosulfuron and pretilachlor) in rice paddy scenarios revealed the capability of the model to accurately predict water and sediment concentrations, as shown by some statistical indicators. Modelling efficiency (EF) values of 0.86-0.99 for the water compartment and of 0.77-0.84 for sediment show the good agreement between predicted and measured concentrations. An "external validation" was performed using measured data for a different herbicide (molinate) applied in a Portuguese paddy rice scenario. A sensitivity analysis for this volatile chemical revealed the influence of some climatic parameters (e.g. temperature) to the model outcomes, such as water and sediment concentrations. This confirmed the capability of DynA model as an efficient tool for the pesticide risk assessment in dynamic scenarios.     

State-space modeling of the relationship between air quality and mortality

A portion of a population is assumed to be at risk, with the mortality hazard varying with atmospheric conditions including total suspended particulates (TSP). This at-risk population is not observed and the hazard function is unknown; we wish to estimate these from mortality count and atmospheric variables. Consideration of population dynamics leads to a state-space representation, allowing the Kalman Filter (KF) to be used for estimation. A harvesting effect is thus implied; high mortality is followed by lower mortality until the population is replenished by new arrivals. The model is applied to daily data for Philadelphia, PA, 1973-1990. The estimated hazard function rises with the level of TSP and at extremes of temperature and also reflects a positive interaction between TSP and temperature. The estimated at-risk population averages about 480 and varies seasonally. We find that lags of TSP are statistically significant, but the presence of negative coefficients suggests their role may be partially statistical rather than biological. In the population dynamics framework, the natural metric for health damage from air pollution is its impact on life expectancy. The range of hazard rates over the sample period is 0.07 to 0.085, corresponding to life expectancies of 14.3 and 11.8 days, respectively.     

Coupling geochemistry with a particle tracking transport model

Coupling geochemistry and transport appears unavoidable since it is rare that either of these two phenomena alone can account for the movement of solutes in groundwater. The chemical model is based on thermodynamic equilibrium. The method used is a Gibbs free energy minimization constrained by mass balances. The model calculates the aqueous speciation, the precipitation and the dissolution of pure minerals or solid solutions. The transport equation is solved by the random walk technique which avoids the problem of numerical dispersion for transport, but may be more time consuming than finite differences or elements if a large number of particles are necessary in order to get a sufficiently “smooth” solution. However, when the chemistry deals with a realistic number of elements (e.g., > 10), the cost of the chemistry computation largely dominates that of transport. Special techniques had to be developed in order to solve problems linked to the conditions present in some of the CEC CHEMVAL tests (boundary with fixed concentrations and very low Péclet numbers). The coupling consists of calculating the exchanges of chemical elements between two populations. The first population is sedentary, constituted by a mesh of fixed cells representing the composition of the solid phase. The other population is nomadic, represented by a set of particles which are advected by groundwater flow. A vector of real numbers is associated with each mobile particle. This vector accounts for the mass of each element dissolved in the moving liquid phase. For this reason, the transport equation is only solved once for the whole set of elements. The main assumptions that were necessary to perform the coupling in a simple way are discussed. Two applications are presented: (1) a verification compared to an analytical solution; and (2) the simulation of a percolation experiment through a sandstone core.     

State-Space Modeling of the Relationship between Air Quality and Mortality

ABSTRACT

A portion of a population is assumed to be at risk, with the mortality hazard varying with atmospheric conditions including total suspended particulates (TSP). This at-risk population is not observed and the hazard function is unknown; we wish to estimate these from mortality count and atmospheric variables. Consideration of population dynamics leads to a state-space representation, allowing the Kalman Filter (KF) to be used for estimation. A harvesting effect is thus implied; high mortality is followed by lower mortality until the population is replenished by new arrivals.

The model is applied to daily data for Philadelphia, PA, 1973-1990. The estimated hazard function rises with the level of TSP and at extremes of temperature and also reflects a positive interaction between TSP and temperature. The estimated at-risk population averages about 480 and varies seasonally. We find that lags of TSP are statistically significant, but the presence of negative coefficients suggests their role may be partially statistical rather than biological. In the population dynamics framework, the natural metric for health damage from air pollution is its impact on life expectancy. The range of hazard rates over the sample period is 0.07 to 0.085, corresponding to life expectancies of 14.3 and 11.8 days, respectively.     

油页岩循环流化床锅炉底渣和飞灰中重金属元素浸出毒性研究

为了研究我国桦甸油页岩65 t/h循环流化床锅炉的底渣和飞灰中重金属元素Cr、Cu、Pb和Zn的赋存状态及不同酸度条件下的浸出特性,分别进行了逐级提取实验和分批浸出的淋滤实验。逐级提取实验结果表明,这4种元素在底渣和飞灰中具有基本相当的赋存状态。硫化物结合态和稳定的残渣态是各元素的主要赋存状态,元素的潜在浸出能力大小表现为:PbCrCuZn,飞灰中各元素的潜在浸出能力大于底渣中的。浸出实验结果表明,元素的赋存状态决定了其浸提能力,浸提液的pH值对各元素浸出能力的影响不尽相同,各元素的浸出能力随浸提时间的延长都会趋于平衡,Cr和Pb的浸出浓度都高于地表水和饮用水的国家标准。     

Occurrence of PCDD/Fs and dioxin-like PCBs in superficial sediment of Portuguese estuaries

Superficial sediments collected from seven estuarine systems located along the Portuguese coast were analyzed for 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs), and 12 dioxin-like polychlorinated biphenyls (dl-PCBs). Total PCDD/F concentration ranged from 4.6 to 464 pg g^?1 dry weight (dw), while that of dl-PCBs varied from 26.6 to 8,693 pg g^?1 dw. In general, the highest PCDD/F and dl-PCB concentrations were associated with densely populated and industrially impacted areas. Additionally, PCDD/F revealed a predominance of octachlorodibenzodioxin (OCDD) to total PCDD/Fs, while PCB 118 was the major contributor to total dl-PCBs. This study provided a global perspective of the contamination status of Portuguese estuaries by dioxin-like compounds and allowed a comparison between the investigated systems and other systems worldwide. PCDD/F and dl-PCB levels found in the collected sediments were lower than those of highly impacted areas from different parts of the globe. Nevertheless, comparison with guidelines and quality standards from other countries indicated that some Portuguese estuarine areas with a high industrialization level present PCDD/F and dl-PCB concentrations in superficial sediment that may constitute a risk to aquatic organisms.     

Interannual patterns of variation in concentrations of trace elements in arms of Octopus vulgaris

Concentrations of essential (copper, iron, manganese, selenium, and zinc) and non-essential (arsenic, cadmium, mercury, and lead) trace elements were measured in arms of Octopus vulgaris. The cephalopods were sampled from commercial fishery landings at two sites on the Portuguese coast in spring 2002 and 2003. Mercury was determined using an Advanced Mercury Analyser Spectrophotometer (AMAS) and other trace elements were measured using inductively coupled plasma-atomic emission spectrometry (ICP-AES). Since high levels of arsenic were detected, identification of the forms present was carried out using high performance liquid chromatography (HPLC) followed by ICP-MS. Mean concentrations of trace elements analysed were in the following order: As > Zn > Fe > Cu > Cd > Pb > Se > Mn > Hg. The results of speciation of arsenic demonstrate that virtually all arsenic was in the arsenobetaine form, which is the less toxic form. The concentrations of several trace elements were generally high in samples from Viana in 2002. Cadmium concentrations were above the legal limit for human consumption in samples from Viana in 2002 and two of these animals also had lead concentrations that exceeded legal limits. Mercury appeared in all samples but levels were within legally defined safe limits. No relationship was detected between trace element concentrations and size or maturity of octopus.     

Distribution and coassociations of trace elements in soft tissue and byssus of Mytilus galloprovincialis relative to the surrounding seawater and suspended matter of the southern part of the Korean Peninsula

The concentrations of Cd, Co, Cu, Cr, Fe, Hg, Mn, Ni, Pb, Sn, Ti and Zn were analyzed by AAS, ICP MS and AFS in soft tissues and byssal threads of Mytilus galloprovincialis from Masan Bay and Ulsan Bay, Korea. Spatial variations in metal concentrations were found. The levels of Cd, Pb, Hg, Cu, Zn, Co and Mn were very high in the mussels from Ulsan Bay (Sts. U1, U2) and comparable with elevated concentrations of these elements in Mytilus sp. reported to date for other geographical areas. Seasonal differences in some metal concentrations were also observed. These variations may be caused by factors such as: a large difference in seawater temperature, food supply for the mussel population and/or freshwater runoff of particulate metal to the coastal water and weight changes brought about by gonadal development and the release of sexual products. Pb, Cu, Zn, Co, Ni, Fe and Mn were more enriched in byssal threads than in the soft tissues, hence the byssus seems to be more sensitive in reflecting the availabilities of trace metals in the ambient waters. Concentrations of trace metals varied with respect to the size of mussels and season, depending on many factors like sexual development, and seawater temperature, etc. The levels of some trace metals in seawater, especially in suspended matter were correlated significantly with those in soft tissues and byssal threads. There were spatial variations in metal concentrations in the soft tissue and byssus attributed to different sources of trace elements located near the sampling sites. There were significant relationships between concentrations of some metals (Cd, Cu, Pb, and Zn) in mussel soft tissues and byssal threads and suspended matter. This suggests that M. galloprovincialis can be used as a sensitive biomonitor for the availabilities of trace elements in the coastal waters off Korea.     

Mixing and transformation of Asian dust with pollution in the two dust storms over the northern China in 2006

To study the mixing and transformation of Asian dust with pollution in the two dust storms over the northern China in 2006, both TSP and PM_2.5 samples were collected at three sites of northern China in addition to the dry deposition samples collected in an episode in Beijing. 23 elements, 15 ions, and 16 PAHs in each sample were analyzed. The two dust storms in northern China were observed in April 8–10 (DS1) and April 16–18 (DS2). Compared to DS2, DS1 was weaker and more polluted with stronger mixing between crustal and pollutant aerosols during their long-range transport. The concentrations of pollution species, e.g. pollution elements, ions, and PAHs were higher in DS1 than that in DS2, while the crustal species showed adverse variation. The correlation between chemical species and Al and between PAH(4) and PAH(5,6) further confirmed the stronger chemical transformation and aerosol mixing in DS1 than that in DS2. Back trajectory and chemical analysis revealed that in DS1 the air masses at Beijing were mostly from southern or southwestern direction at lower altitude with much more pollution, while in DS2 the air masses were mostly from the northwestern and northern direction with dust mainly, which explained why there was a stronger mixing of dust with pollution aerosol in DS1 than that in DS2 over Beijing.     

Elemental distribution in the edible leaves of Celosia trigyna from the western and northern regions of Nigeria

Celosia trigyna, which belongs to the plant family Amaranthaceae, is a plant used in traditional medicine to treat several conditions such as sores, chest pains, diarrhoea and menstrual cramps in many countries in Africa. It is also consumed by the local people in Nigeria as soups, sauces and stews. In this study, the distribution and bioaccumulation of the elements in C. trigyna species and growth soil from the western and northern regions of Nigeria was investigated to determine the effects of geographical location on the uptake of elements by the plant. Elemental concentrations in the leaves from the western region were found to be in decreasing order of Ca?>?Mg?>?Fe?>?Mn?>?Zn?>?Cu?>?Pb?>?As?>?Ni. Concentrations of elements in the leaves from the northern region were found to be in decreasing order of Ca?>?Mg?>?Fe?>?Mn?>?Zn?> Cu?>?As?>?Pb?>?Ni?>?Co?>?Cd. Proximate analysis of leaves from both regions compared well with the recommended dietary allowance making the leaves safe for human consumption. Principal component analysis was used to group elements having the same sources irrespective of their geographical locations. Cd, Co and Cr were not detected in the leaves from the western region. Concentrations of As and Pb were above maximum permissible limits in both regions, while Ayegunle and Bida (in the northern region) had the highest concentrations of Cd. The high level of these toxic metals may be attributed to anthropogenic activities. It is therefore important that the Nigerian agricultural extension system emphasizes the dangers of heavy metal contamination in leafy vegetables to farmers. Activities of the manufacturing industries in the study area should be adequately monitored under standard environmental protection laws.