Cluster analysis of inorganic elements in particulate matter in the air environment of an equatorial urban coastal location

Concentrations of nine inorganic elements (Na, Zn, Ca, Fe, Ni, Mn, Cu, Cd and Al) in particulate matter (PM₁₀) in the air of an equatorial urban coastal location during 2009 were studied during summer and winter monsoon seasons using high-volume sampling techniques. Atomic absorption spectrophotometry was used to analyse the samples. The concentrations of most inorganic elements were higher during summer than winter, except for Cu and Zn. The main inorganic elements in PM₁₀ are Na, Zn and Ca. High concentrations of Na and Ca are due to marine aerosols. Analysis of enrichment factors showed that inorganic elements are from non-crustal sources. Cluster analysis identified five clusters in the summer and six in the winter: (1) PM₁₀–Ni, (2) Zn–Na, (3) Fe–Cu–Ca–Cd, (4) Mn and (5) Al for summer; and (1) PM₁₀, (2) Zn, (3) Fe–Ni, (4) Cu–Ca–Na–Cd, (5) Mn and (6) Al for winter. Combining both correlation and cluster analysis, it was found that Fe–Cu–Cd was from industry/vehicle emissions, Zn was from resuspended soil, Mn was from metallurgical processes, Ni was from a nearby power plant and Al was from crustal sources. Inorganic element concentrations could be a good indicator of local sources of PM₁₀.     

Distribution of metals in mechanical fractions of soils from a lake catchment in Venezuela

Soil samples were collected from both the surface and at depth from the lowlands around Lake Valencia and from the adjacent mountains. This paper reports results for Al, Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb and Zn in mechanical fractions of the soils. Lowland soils, developed on lacustrine sediments, show a predominance of medium- to fine-grain size fractions whereas the shallow mountain soils show the highest percentage of particles in the coarse to medium fractions. Concentrations of most of the elements investigated increased toward finer particle sizes. The generally higher metal concentrations in lowland soils compared with mountain soils are consistent with release by weathering in the uplands and accumulation in the lowlands. The presence of carbonates derived from ubiquitous shelly material in the lowland soils may explain increases of Ca and Mg in labile fractions. In the lowland area, there is little evidence for the translocation of metals in the soil profiles, despite the high rainfall of a tropical climate, and the calcareous nature of these soils could account for the immobility of metals.     

Mobilization of different metals between Tamarix parts and their crystal salts – soil system at the banks of river Nile,Aswan, Egypt

In order to study the relation of the mobility and distribution of metals between Tamarix parts and their crystal salts – soil system, different experiments were conducted with plant-rich and plant-free soils at the banks of river Nile, Aswan, Egypt. For these purposes, Tamarix top and subsoil samples near and far from the plant were collected from six different locations at the banks of river Nile. Elemental analysis of Fe, Mn, Ca, Mg, Cr, Cu, Ni, Zn, Cd and Pb in soil, and in different parts of Tamarix and their crystal salt samples was carried out by atomic absorption spectrometry, whereas Na and K were measured by atomic emission spectrophotometry. The bioavailability of metals in the soil samples was evaluated by determining their contents using sequential extraction single-step, providing higher metal concentrations in occluded Fe/Mn oxide fraction. The ratio of heavy metal concentrations in topsoil to that in subsoil enhancement (RTE) ranged from 0.67 to 4.4 and 0.22 to 4.61 for soil Tamarix and soil free from plant, respectively for all measured total element concentrations. Data indicate that the mobility expressed as transfer factor (TF) was obtained as Fe?>?Mg?>?Cr?>?Mn?>?Ca?>?K?>?Na, for Tamarix leaves. The major part of accumulated Na in Tamarix is retained in the plant leaves, while roots accumulated high concentration of Co.     

Trace elements in particulate matter of ambient air at petroleum filling stations

Size segregated suspended particulate matter (PM_2.5 and PM_10-2.5) in air at four major petroleum-filling stations in Ile-Ife, Nigeria, were monitored using double staged “Gent” stacked samplers to assess variations in mass loads and elemental concentrations of 25 elements. Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr, Zr, Cs, Ta, W, and Pb were determined in both fractions by external ion beam proton-induced X-ray emission technique. Enrichment factors and pollution indices were calculated and results revealed that most elements were anthropogenic in both fractions with concentrations exceeding the World Health Organization guideline standards.     

Scalp hair metal analysis in the assessment of the occupational exposure of arc welders

Eleven metals (Ca, Mg, Fe, Zn, Cu, Mn, Cd, Co, Cr, Ni and Pb) were estimated in hair samples of metal arc welders and a control group with the same socioeconomic background. Nitric acid–perchloric acid wet digestion procedure was adopted for the estimation of endogenous metal contents by ICP-AE technique. The study exhibited the following increasing order of the metal concentrations: Cd??1, dry weight, respectively. On average, the levels of Mn, Ni, Pb and Fe were found to be 1.5–2.4 times higher in the hair of welders compared with controls. Besides age and exposure which were strongly correlated, Cu–Mg, Mn–Mg, Ca–Co and Cd–Zn also showed significantly positive correlations. The identification of metal sources, done by cluster and principal component analyses, revealed four factors: age and exposure; Cu, Mg, Mn and Fe; Ca and Co; Cd, Zn, Ni and Pb. High levels of Fe were found to have a depleting impact on Co levels. The arc welders were feared to accumulate heavy metals in their bodies due to long-term endogenous exposure.     

Ombrotrophic peat as a medium for historical monitoring of heavy metal pollution

Knowledge of historical trends in heavy metal deposition can aid the study and impact prediction of contemporary pollution. For this purpose, analysis of ombrotrophic peat cores has proved a valuable complement to other sedimentary analyses. However, doubts still remain concerning the mobility of heavy metals in peat. The debate cannot be resolved until the behaviour of these elements in peat is better understood. Peat cores were collected from hollows and hummocks on Ringinglow Bog in the southern Pennines. The cores were sliced into contiguous 1-cm slices. Samples were analysed for total concentrations of major elements (Al, Ca, K, Mg, Na) and trace metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn) using atomic absorption spectrophotometry. Multivariate statistical analysis was conducted on the data. Preliminary results indicate relatively high concentrations of Cd, Cu, Fe, Pb and Zn reflecting the influence of industrial activities in Sheffield and Manchester. As aluminium, cadmium, copper, lead and zinc exhibit similar profiles they may be suitable surrogates for monitoring historical pollution. However, other elements (e.g. Fe, K, Mn, Na) are clearly influenced by bog hydrology or plant translocation and would be inappropriate monitors.     

耕地土壤中交换态钙镁铁锰铜锌相关关系研究

应用主成份分析、聚类分析和相关性分析对沈阳市郊区1994个耕地土壤样本(0-20cm)的交换态钙、镁、铁、锰、铜、锌含量进行研究，结果表明，影响钙与镁、铁与锰、铜与锌分布的主因子分别在相同的主成份组中，钙与镁、铁与锰、铜与锌之间的相关系数较大，铁、锰、铜、锌之间均为极显著正相关关系，钙与铁、锰、铜、锌均为负相关关系，说明元素的生物地球化学属性对其地理分布有较大的影响。     

Assessment of metals in soil extracts and their uptake and movement within Tamarix nilotica at Lake Nasser banks,Egypt

This study aims to determine heavy-metal levels in soil from the banks of Lake Nasser, the ability of Tamarix nilotica to accumulate such metals from soil and hence its potential for phytoextraction. Soil and Tamarix samples were collected from the banks of four bights around Lake Nasser and analysed for Fe, Mn, Ca, Mg, Cr, Cu, Ni, Zn, Cd and Pb by atomic absorption spectrometry, whereas Na and K were measured by atomic emission spectrophotometry. Three different methods of extraction were used for the soil samples. Lead, copper and zinc were equally distributed between the exchangeable phase and Fe/Mn oxide-bound form, while other measured metals were mainly present in the Fe/Mn oxide fraction. With the exception of iron, all metals studied showed total concentrations within the geochemical background values. T. nilotica exhibited elevated concentrations of Na (36.2–48.5?mg?g^?1) and K (2.74–4.33?mg?g^?1) in stems, and relatively high concentrations of Pb, Cd and Co (0.39–1.03?µg?g^?1, 0.24–1.3?µg?g^?1 and 1.94–5.3?µg?g^?1, respectively) are found in plant leaves. Bioaccumulation factors of Na and K (9.3 and 12.63, respectively) were high in T. nilotica stems. While the bioaccumulation of Pb, Cd, Co and Ni (2870.1, 2035.4, 10.5 and 5313.2, respectively) was high in plant leaves, Fe, Mn, Ca and Mg were accumulated relatively equally in plant stems and leaves. T. nilotica was found to secrete high amounts of Na, Ca and K, in addition to small amounts of all accumulated metals except Cd and Cu. These secreted metals appeared as salt crystals (67.5% Na; 25.8% Ca; 5% Mg; 1.5% K and 0.16% trace and minor elements) on the plant surface. The concentrations of all the metals studied in T. nilotica were higher than in the salt crystals. Statistical analysis of the database suggests bioaccumulation of these metals from soil to T. nilotica. This reflects the importance of using T. nilotica as a model in the phytoremediation process as an established environmental clean-up technology.     

Annual production and molecular weight as an influential factor for environmental distribution of chemicals — a case study in Japan

The changes promoted by treatment of a highly polluted soil with sulphuric acid or calcium hydroxide for changing its pH value are studied by controlling physical properties (particle size, TGA and DTA curves), evolution of metal species (exchangeable, as carbonates, related to Fe‐Mn oxides, linked to organic matter and residual) and metal uptake by plant cultures. Metal contents were determined, after wet digestion with HF—HNO₃—HC1O₄ when necessary, by AAS (Ca, Mg, Cu, Pb, Mn, Fe, Zn) or emission (Na, K). The treatment of soil with successive amounts of sulphuric leads to changes in particle size, hydration properties and exothermic peak for organic matter combustion. Very small changes were, however, detected in the alkaline treatment of soil. Soil treatments do not have practical influence on speciation of some metals (Na, K, Mg, Pb, Mn, Fe), but the intensity of the acid treatment leads to both an increase in the Cu extraction and a decrease in the Ca solubilization, probably through gypsum formation. In the case of zinc a maximum solubility in the middle of the range of acid treatment was observed. The comparison among extractants shows solubilities high for two pollutants (Pb, Cu), associated mainly to Fe—Mn oxides and organic matter, and low for two macrocomponents (Fe, K). The rest of metals, basically present in soil as carbonates or oxides, have intermediate extractions. Pot cultures weights depended mainly on both the treatment of soil (poor development in the more acid sample and drainage difficulties in the rest of acid treatments) and the situation (very low weights in laboratory runs as compared with outside), but the irrigation with water or a diluted sulphuric acid solution (at pH = 4.0) did not produce significant weight changes. Tendencies to increase plant pollution were observed for smaller soil pH, acid irrigation and probably for outside cultures, due to uptake by leaves.     

Assessment of metals in soil extracts and their uptake and movement within Tamarix nilotica at Lake Nasser banks, Egypt

This study aims to determine heavy-metal levels in soil from the banks of Lake Nasser, the ability of Tamarix nilotica to accumulate such metals from soil and hence its potential for phytoextraction. Soil and Tamarix samples were collected from the banks of four bights around Lake Nasser and analysed for Fe, Mn, Ca, Mg, Cr, Cu, Ni, Zn, Cd and Pb by atomic absorption spectrometry, whereas Na and K were measured by atomic emission spectrophotometry. Three different methods of extraction were used for the soil samples. Lead, copper and zinc were equally distributed between the exchangeable phase and Fe/Mn oxide-bound form, while other measured metals were mainly present in the Fe/Mn oxide fraction. With the exception of iron, all metals studied showed total concentrations within the geochemical background values. T. nilotica exhibited elevated concentrations of Na (36.2-48.5 mg g^-1) and K (2.74-4.33 mg g^-1) in stems, and relatively high concentrations of Pb, Cd and Co (0.39-1.03 µg g^-1, 0.24-1.3 µg g^-1 and 1.94-5.3 µg g^-1, respectively) are found in plant leaves. Bioaccumulation factors of Na and K (9.3 and 12.63, respectively) were high in T. nilotica stems. While the bioaccumulation of Pb, Cd, Co and Ni (2870.1, 2035.4, 10.5 and 5313.2, respectively) was high in plant leaves, Fe, Mn, Ca and Mg were accumulated relatively equally in plant stems and leaves. T. nilotica was found to secrete high amounts of Na, Ca and K, in addition to small amounts of all accumulated metals except Cd and Cu. These secreted metals appeared as salt crystals (67.5% Na; 25.8% Ca; 5% Mg; 1.5% K and 0.16% trace and minor elements) on the plant surface. The concentrations of all the metals studied in T. nilotica were higher than in the salt crystals. Statistical analysis of the database suggests bioaccumulation of these metals from soil to T. nilotica. This reflects the importance of using T. nilotica as a model in the phytoremediation process as an established environmental clean-up technology.     

An exploratory study with the proton microprobe of the ontogenetic distribution of 16 elements in the shell of living oysters (Crassostrea virginica)

Study of the chemical composition of shell of exoskeletonous organisms in the past has required the sacrifice of the organism. Because the beam of the proton microprobe is relatively nondestructive and analyzes the surface layer of the shell, organisms do not have to be killed. The present paper presents results of a preliminary experiment in which distribution of elements (Na to Sr) in shell of living juvenile oysters, Crassostrea virginica (Gmelin), was studied in situ with a proton microprobe at monthly intervals for four months. The relative concentration of 16 elements was measured in the newly deposited prismatic edge of the right valve of three oysters reared in controlled laboratory conditions. Na, Mg, Al, Si, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Cu, Zn, Br, and Sr were detected in concentrations as low as a few parts per million relative to the concentration of standards added to pure CaCO₃. Concentration of elements varied nominally among shells of the three individual oysters and in their successive ontogenetic stages. Fluctuations in concentration of Na, Mg, S, Cl, Ca, Mn, Fe, Cu, and Zn were generally similar in the two normally growing oysters, but differed from those in the oyster that stopped growing. Trends in concentration of Al, Si, and Sr were similar in the three oysters: those of Br were variable. Relative concentrations of Na, Cl, S, Mn, Fe, and Zn increased slightly with age of oysters, that of the other elements stayed relatively constant. Concentration of most elements was higher in shell than in seawater. Variable concentrations, especially of Na, Cl, and Si in valve edges, tend to support the hypothesis of earlier workers that separate mineral phases are present as impurities entrapped within the shell during calcification.     

Distribution of metallic compounds between plants and soils∗

Distribution of metallic constituents between soil and aerial parts of wild plants has been discussed by using relative ionic impulsions, i/I, defined as functions of concentrations of metallics ions, being i = [M]^1/2M, z_M the oxidation state of considered metal and I = S i the summation of contribution of metals. For this calculation metals were divided into two groups leading to ^I macro (K, Na, Ca, Mg, and Mn, elements accumulated in aerial parts) and to I _Micro (Fe, Cu, Zn, Co and contaminants accumulated in roots). Relative ionic impulsions may be attributed to an electric potential gradient and show if an active or passive uptake is happening. For macroelements linear relationships were obtained for Mg‐K (global active uptake) and Na‐Mn‐Ca (global passive uptake) with inverse slopes. Passive ions seem to be used as counter ions for helping active assimilation. Calculated potential gradient was close to 20 mV. The same situation was found for microelements and pollutants, where Fe is taken passively helping assimilation of the rest (Cu, Zn, Co, Cd, Pb, Ni and Cr) with a potential gradient close to 13 mV. Influences of other ecological segments (rainfall, dry deposition, airborne dust and irrigation), as well as additions for amending contaminated soils are finally discussed.     

排水对三江平原沼泽湿地土壤中化学元素的影响

以三江平原沼泽湿地生态试验站为研究基地 ,选择典型采样点 ,对排水沟土壤、沼泽土壤、沼泽化草甸土壤 (共有 6个采样点 ,2 8个样品 )进行测试 ,分析土样中主要离子 (HCO3- 、Cl- 、NO3- 、SO4 2 - 、Ca2 +、Mg2 +、K+、Na+)含量、重金属 (铁、锰、锌、铜 )含量、营养元素含量、有机质含量以及土壤pH值 ,研究沼泽排水对沼泽土壤中的化学元素含量的影响。研究结果表明 ,排水使沼泽土壤丧失大量的化学元素     

铜镉复合胁迫下温度对小麦幼苗生长及其对铜、镉和矿质营养元素吸收与各元素在亚细胞分布的影响

为了研究重金属复合胁迫下温度变化对陆生植物的毒性效应的影响,实验采用水培的方法,设置对照和Cu-Cd复合胁迫(10 μmol·L1 Cu+10μmol·L-1Cd)2个处理,每个处理分别设置3个不同的培养温度(8/4℃、25/20℃和35/30℃),对小麦进行48 h的暴露实验,测定小麦幼苗的生长及其对重金属和矿质营养...     

Speciation of Heavy Metals in Floodplain and Flood Sediments: a Reconnaissance Survey of the Aire Valley, West Yorkshire, Great Britain

A five-step sequential extraction technique was used to determine the chemical association of heavy metals (Pb, Zn, Cu and Cd), with major sedimentary phases (exchangeable, surface oxide and carbonate, Fe and Mn oxides, organic and residual metal ions), in samples from floodplain and recent flood sediments of the River Aire, West Yorkshire. Analysis indicates that metals Pb and Zn are primarily associated with the Fe and Mn oxides, Cu with the organic fraction and Cd with exchangeable and surface oxide and carbonate metal ions. Knowledge of the chemical speciation of heavy metals in river sediment, despite the procedure's inherent limitations, facilitates an understanding of their bioavailability, storage and remobilisation in floodplain and river channel environments.     

Metals in Cancer irroratus (Crustacea: Decapoda): Concentrations,concentration factors,discrimination factors,correlations

Nine metals were analysed in whole specimens of the decapod crustancean Cancer irroratus, and three in the exoskeleton of Carcinus maenas. In terms of concentrations (expressed as parts per millions) and concentration factors, 2 groups of metals could be distinguished in Cancer irroratus: Zn, Cu, Fe and Mn in one group, Ca, Mg, Sr, Na and K in the other group. Na excepted, all the metals had concentration factors significantly higher (P<0.01) than 1. The concentration factor of Na was significantly lower (P<0.01) than 1, demonstrating the existence in C. irroratus of a barrier to the movement of Na into the crustacean from its environment. Studies of coefficients of discrimination (D), in C. irroratus, for metals considered in pairs, showed, in each case that D was significantly different (Plt;0.01) from 1. Only the discrimination factor between, Zn and Mn was less significantly different (0.05lt;Plt;0.1) from 1. Correlations were made between the concentrations of metals and other parameters: water content, size, and ash content. Significant correlations were found, especially in the cases of the pairs Ca?Sr, Na?K, Cu?Zn, and Mn-animal size.     

The Nutrient Status of Some Graminaceous Species in Britain. 2. Deschampsia Flexuosa (L.) Trin

Above-ground biomass of Deschampsia flexuosa from 40 sites throughout Britain was analysed for concentrations of elements (N, P, K, Ca, Mg, Fe, Mn, Cu, Zn and Na), with matching analyses of nutrient levels in the soils, together with pH and LOI. Seasonal variation in the nutrients was also studied in detail at one of the sites. the grass was found on acid sites ranging between pH 3.1 and 4.7. the soil humus content varied widely, and there were significant correlations between that and elements (N, P, K, Ca, Mg, Zn and Na) in the soil. Concentrations of zinc and manganese in the plant material were the only elements that significantly correlated with extractable levels in the soils. Tissue concentrations of nitrogen, phosphorus, and potassium declined throughout the growing season, whereas the other elements showed a tendency to build up until the end of September. Calcium, magnesium and manganese concentrations then declined as growth ceased. the results are compared with above-ground concentrations of minerals in other plants and the growth strategy of this perennial grass.     

Fractionation of trace metals (Mn,Zn, Cu,Pb) in Red Sea sediments,Gulf of Aden,Yemen

A sequential extraction technique was applied to estimate the chemical association of Mn, Zn, Cu and Pb in five chemical phases (exchangeable, carbonate, Fe–Mn oxides, organic matter and residual) in sediments of the Gulf of Aden, Yemen. The results indicated that a higher level of Mn was associated with the residual fraction (natural sources) than the non-residual fraction (anthropogenic sources). Zn fractionations revealed that it was associated more with Fe–Mn oxides and organic fractions than exchangeable and carbonate fractions. Most of the Cu was present in the residual form (60–72%) except for in the main port area (zone III), where it was associated with the organic phase (77% of the total Cu content, the organic matter content was 5%). Similarly, most Pb was bound in the residual fraction (56–71%) except the main port area where ～ 62% of the total Pb was bound in non-residual fractions. It was also found that the Pb concentration in the exchangeable fraction was very high compared with other metals. The risk assessment code for the metals showed a low risk for Zn and Cu, but low to medium risk for Mn. Fractionation of Pb showed medium risk at most of the regions except at the eastern area, which revealed a high risk for the aquatic environment.     

Improved characterisation of inorganic components in airborne particulate matter

We set up a microanalytical procedure for non-volatile ions by ion chromatography (IC) and for elements by energy-dispersive X-ray fluorescence (ED-XRF) and inductively coupled plasma optical emission spectroscopy (ICP-OES). We analysed NO₃, SO₄, NH₄, Na, Mg, Ca, Fe, S, Zn, As, Cd, Cu, Mn, Ni, Pb, Sb, Se, Ti, and V. The use of complementary techniques yields reliable data for both trace and crustal elements, overcoming the analytical restrictions characteristic of the individual techniques. Some elements determined by two or by all three techniques can be used as data quality markers. The application of the procedure to a short PM_2.5 monitoring campaign is also described, aimed to the identification of fireworks tracers.     

Nutritionally relevant elements in staple foods: influence of arable site versus choice of variety

Eighteen representative sites for the Austrian grain-growing and eight for the potato-growing zones (soils and crops) were investigated. On each site, total element contents (B, Ba, Ca, Cd, Co, Cu, Fe, K, Li, Mg, Mn, Mo, Na, P, Sr and Zn) were determined in 4–12 varieties of winter wheat (n = 136), 6 varieties of spring durum wheat (n = 30), 5 varieties of winter durum wheat (n = 15), 7 varieties of rye (n = 49), 5 varieties of spring barley (n = 30) and 5 varieties of potatoes (n = 40). Element accumulations in grain species and potato tubers varied significantly with site conditions, with the main exceptions for B in potatoes and wheat as well as for Zn, Cu and Co in durum wheat. On average, across all investigated sites, differences in varieties occurred concerning the elements Ca, Cd, Ba, Sr and Zn (except Zn in potatoes and winter durum). A rough estimation revealed that an average Austrian consumer of wheat, rye and potatoes meets more than 50% of the needs of daily element intake for K, P and Mg, between 36 and 72% for Fe, Zn and Cu, and more than 100% for Co, Mo and Mn. In particular, the elements Ca and Na have to be added from other sources.