The use of a sequential leaching procedure for heavy metal fractionation in green liquor dregs from a causticizing process at a pulp mill

A five-stage sequential leaching procedure was used to fractionate heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Ni, Co, As, V, Ba and Ti) in green liquor dregs into the following fractions: (1) water-soluble fraction (H2O), (2) exchangeable fraction (CH3COOH), (3) easily reduced fraction (HONH3Cl), (4) oxidizable fraction (H2O2 + CH3COONH4), and (5) residual fraction (HF + HNO3 + HCl). The green liquor dregs were derived from a causticizing process at a pulp mill at Kemi, Northern Finland. According to the leaching studies, the leachability of heavy metals in the water-soluble fraction varied between 0.5 and 2 mg kg(-1) expressed on a dry weight (d.w.) basis, indicating relatively low bioavailability of the metals. However, the concentration of Mn (2065 mg kg(-1); d.w.) showed a strong and of Zn (17.6 mg kg(-1); d.w.), Ni (39.7 mg kg(-1); d.w.) and Ba (32.0 mg kg(-1); d.w.) slightly tendency to be extracted in the exchangeable fraction. In addition, Zn, Mn, Ni, Co, V and Ba showed clear leachability in the easily reduced fraction, as well as Cd, Cu, Cr, Zn, Mn, As and Ba in the oxidizable fraction. For Cd, Cu, Cr, Zn, Mn, Ni, Co, Ba and Ti, the sum of leachable heavy metal concentrations in fractions 1-5 agreed relatively well with the "total" heavy metal concentrations. Recoveries of the sum of fractions 1-5 were 84-56% of those obtained by the US EPA method 3052 (i.e. concentrations obtained after microwave oven digestion with a mixture of HF and HNO3).     

Source characterization for atmospheric trace metals over Kiel Bight

Atmospheric concentrations of Na, Al, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Rb, Sr, Ba and Pb are reported for 59 weekly air filter samples collected over the Kiel Bight. The contributions of sea salt, mineral dust and anthropogenic emissions to each of these elements were assumed to be represented by the concentrations of indicator elements, which were Na, Al and Zn, respectively. Based on this assumption a multiple regression analysis was applied to the concentration data. The results showed that atmospheric sea salt contributed significantly only to Sr and, of course, Na. Considerable portions of Al, K, Ca, Ti, Cr, Mn, Fe, Rb, Sr and Ba were derived from mineral dust. Anthropogenic sources were responsible for total V, Ni, Cu, Zn, As and Pb, and there was an anthropogenic component for most of the other elements.Moreover, the anthropogenic contribution was characterized by a nearly constant composition with respect to Ca, Ti, Cr, Mn, Fe, Cu, Zn, As, Rb, Sr, Ba and Pb, indicating that trace metals over the Kiel Bight are mainly derived from one source area. This conclusion was confirmed by correlating anthropogenic trace metal concentrations with the wind direction. A 40° wind sector directed to the south of the sampling site was identified as the major pathway for the transport of anthropogenic trace metals to the Kiel Bight.     

Mosses and lichens as biomonitors of trace metals. A comparison study on Hypnum cupressiforme and Parmelia caperata in a former mining district in Italy.

Samples of the moss Hypnum cupressiforme and the epiphytic lichen Parmelia, caperata were collected during the summer of 1999 in an area (Colline Metallifere, central Italy) intensively exploited in the past for metals (Cu, Fe, Pb, Zn) and currently for geothermal resources. Lichens were more sensitive than mosses to emissions of S compounds near geothermal fields and abandoned sulphide ore smelting plants. Comparison of elemental compositions of the two cryptogamic species from the same sampling sites showed significantly higher concentrations of lithophile elements (Al, Cr, Fe, Mn, Ni, Ti) in the moss and atmophile elements (Hg, Cd. Pb, Cu, V, Zn) in the lichen. Patterns of bioaccumulation of elements throughout the study area were quite similar for widespread pollutants such as S, B, As, Zn, Cr and Ni, but the lichen and the moss showed different distribution patterns of Hg, Cd and other elements subject to long-range atmospheric transport. These results are due to differences in the morphology and ecophysiology of mosses and lichens and indicate that these organisms cannot be used interchangeably as biomonitors of metals in areas with mineral deposits.     

应用地质累积指数评价抚顺市PM10中元素的污染

2006-2007年采暖季、风沙季和非采暖季分别在抚顺市的6个采样点采集PM10样品,用等离子体原子发射光谱(ICP-AES)法测定样品中Ti、Al、Mn、Mg、Ca、Na、K、Cu、Zn、As、Pb、Cr、Ni、Co、Cd、Fe、V等17种元素的含量,并用地质累积指数对其污染状况进行初步评价。结果表明:(1)从PM10中元素在不同采样点的含量看,抚顺市PM10中Ti、Mn、Mg、Cu、Zn、Pb、Cr、Ni、Co这9种元素在各采样点间的差别较大;Al、Ca、Na、K、As、Cd、Fe、V这8种元素差别较小。(2)从PM10中元素在不同采样季的含量看,抚顺市PM10中Mn、Mg含量的季间差别较大,其余15种元素季间差别较小。(3)Zn、Cd污染较重;Ti、Al、Mg、Ca、Na、K、As、Fe和V污染较轻;其他6种元素在6个采样点和3个采样季污染程度差别较大。(4)水库采样点各元素污染级别均不是最高;新华采样点PM10中Cu、Zn、Pb、Cr、Ni、Co、Cd污染级别均较高。(5)3个采样季PM10中Cd、Zn污染均较重,属于重度或严重污染;在采暖季PM10中Cu、Pb、Cr的地质累积指数较风沙季、非采暖季大;在非采暖季PM10中Mn、Co受到的污染比采暖季和风沙季稍严重。     

Influence of angular exposure and proximity to vehicular traffic on the diversity of epiphytic lichens and the bioaccumulation of traffic-related elements

This study investigated the influence of angular exposure and distance from vehicular traffic on the diversity of epiphytic lichens and the bioaccumulation of traffic-related elements in a town of central Italy. An Index of Lichen Diversity (ILD) was calculated on the street-facing and the opposite side of road-lining trees and in a urban park 250 m away, and the content of selected trace elements (Al, Ba, Ce, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V, and Zn) was determined in samples of the lichen Punctelia borreri (Sm.) Krog growing on tree bark, both on the exposed and opposite sides. ILD increases with distance from traffic emissions. However, at the site with vehicle traffic, non-nitrophilous lichens decreased while nitrophilous ones increased. The concentration of the traffic-related elements Ba, Cr, Cu, Mn, Sb, and Zn accumulated in thalli of P. borreri was higher on roadside trees than in trees from the urban park. ILD was not affected by the angular exposure to the road and the bioaccumulation of traffic-related elements was similar in lichens from the side of the bole exposed to traffic emissions and particulate resuspension and from the opposite side. The angular exposure in respect to the traffic source does not influence trace element accumulation. These results are important when using lichens for biomonitoring purposes, both for planning future studies and for the reliability of the interpretation of past surveys that do not report information about the angular exposure of the collected lichen material.     

Comparison between the accumulation capacity of four lichen species transplanted to a urban site

The capacity to accumulate trace elements from the atmosphere of the lichens Hypogymnia physodes, Parmelia sulcata, Pseudevernia furfuracea and Usnea gr. hirta transplanted to an urban site of N Italy was compared. Twenty-nine elements (Al, As, Br, Ca, Cd, Ce, Cl, Co, Cr, Cs, Cu, Fe, Hg, I, K, La, Mg, Mn, Ni, Pb, Rb, Sb, Sc, Se, Sm, Th, Ti, V, Zn) were analyzed by Instrumental Neutron Activation Analysis (INAA) and Electro-Thermal Atomic Absorption Spectroscopy (ET-AAS). The ratio between the concentrations of each element in exposed samples to that of control samples (exposed-to-control ratio and EC ratio) was used to investigate the accumulation rates of lichen thalli. The results showed that in general elements did not exhibit well defined trends, but rather showed fluctuations, and indicated that H. physodes, P. furfuracea and U. gr. hirta have a similar accumulation capacity, while that of P. sulcata is lower.     

Comparison of the heavy metal bioaccumulation capacity of an epiphytic moss and an epiphytic lichen

This study compared the heavy metal bioaccumulation capacity in the epiphytic moss Scorpiurum circinatum and the epiphytic lichen Pseudevernia furfuracea, exposed in bags for 3 months in the urban area of Acerra (S Italy). The content of Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Ti, V, and Zn was measured by ICP-MS. The results showed that both species accumulated all the heavy metals assayed. The moss had the highest bioaccumulation capacity for all metals and showed a more constant and linear accumulation trend than the lichen. Intra-tissue heavy metal bioaccumulation was assessed by X-ray microanalysis applied to ESEM operated in high and low vacuum and ESEM modes.     

Element content in tissues of four rodent species sampled in the Geysers geothermal steamfield

Liver and kidney tissue samples from four rodent species collected in the Geysers geothermal steamfield of northern California were analyzed for content of 28 elements. Element concentrations in samples from the developed region of the Geysers were compared with samples from undeveloped reference regions to determine the influence of geothermal power development on element content in small mammal tissues. Eight elements (B, Ca, Cu, Mg, Mn, P, Sr, Ti) were enriched in samples from the Geysers, 12 (Ag, Al, Co, Cr, Fe, K, Mo, Na, Ni, Pb, Si, Zn) were decreased within the Geysers, Ba and Li were inconclusive, and six (As, Be, Cd, Hg, Sn, V) were below the minimum analytical limits. The longest-lived species (Neotoma fuscipes) had the greatest occurrence of statistically significant differences in element content. Sites in grassland habitat produced more significant differences in element content than either chaparral or streamside habitats for samples from Peromyscus maniculatus. Peromyscus boylii and P. truei provided additional data, but no distinct advantages for element monitoring. The data indicate regional influences from geothermal power development on element levels in rodent tissues.     

Volcanic and anthropogenic contribution to heavy metal content in lichens from Mt. Etna and Vulcano island (Sicily)

Major and trace element concentrations were determined in two lichen species (Parmelia conspersa and Xanthoria calcicola) from the island of Vulcano and all around Mt. Etna. In both areas, the average concentrations of Al, Ca, Mg, Fe, Na, K, P and Ti are substantially greater than those of other elements. Several elements (Br, Pb, Sb, Au, Zn, Cu) resulted enriched with respect to the local substrates. The Br and Pb enrichment factors turned out to be the highest among those calculated in both areas. Data indicate that mixing between volcanic and automotive-produced particles clearly explains the range of Pb/Br shown by lichen samples. Sb is also enriched, revealing a geogenic origin at Vulcano and a prevailing anthropic origin at Mt. Etna. Distribution maps of the enrichment factors show a generalized enrichment of Au and Zn near Mt. Etna, whereas Cu appears to be enriched prevalently in the NE-SE area. The highest levels of Au and Cu at Vulcano occur E-SE from the craters, following the prevailing wind direction.     

Atmospheric trace element deposition: principal component analysis of ICP-MS data from moss samples

Data from a Norwegian survey on atmospheric deposition, including 33 elements in 495 moss samples collected in 1990, are presented. The biomonitor moss used was Hylocomium splendens, and the analyses were carried out by ICP-MS. Principal component analysis is used to identify possible sources of the elements determined in the mosses. Dominant factors represent long-range atmospheric transported elements (Bi, Pb, Sb, Mo, Cd, V, As, Zn, Tl, Hg, Ga), windblown mineral particles (Y, La, Al, Li, U, Th, Ga, Fe, V, Cr), local emission sources (Ni, Cu, Co, and As; Zn, Cd, and Hg; Fe, Cr, and Al), transport from the marine environment (Mg, B, Na, Sr, Ca), and contribution from higher plants (Cs, Rb, Ba, Mn). Comparison of the results with similar surveys from 1977 and 1985 show a decreasing contribution of most long-range transported elements to southern Norway.     

Biomonitoring using the lichen Hypogymnia physodes and bark samples near Zlatna, Romania immediately following closure of a copper ore-processing plant

Lichen transplants were established along a 40km transect centred on a large mine waste dump close to Zlatna town centre, two weeks after closure of a major industrial source, to compare spatial patterns of element concentrations in lichen and bark samples. After 3 months of exposure, spatial patterns of 4 element concentrations (Pb, Cu, Zn and Fe) in transplants confirmed deposition due to a point source 'Zlatna influence'. Cu and Pb reached concentrations 8 and 4 times, respectively, higher than samples transplanted in the 'background' site, and over 200 (Cu) and 2000 (Pb) times higher relative to 'background' bark. Ten out of 15 elements analysed reached highest concentrations in bark. Spatial patterns confirmed long-term pollution for 6 elements (Pb, S, Fe, Cu, Zn and Ba). The study provides a model baseline to monitor recovery following closure of major industrial sources and highlights the importance of considering biogeochemical processes when interpreting metal concentrations.     

Analysis of essential and non-essential trace elements in the organs of a mother–fetus pair of spotted seals (Phoca largha) from the Sea of Japan

Environmental Science and Pollution Research - Concentrations of 22 essential and non-essential trace elements (Be, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, Sb, Ba, Tl, Pb, Th, U, and...     

Testing the Bergerhoff method to determine the bulk deposition loads of 49 elements

The suitability of the simple and rather cheap Bergerhoff method for the determination of bulk deposition loads of 49 elements was tested. The method is suitable for the following elements: Ag, Al, As, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, Ge, In, K, La, Li, Mg, Mn, Mo, Na, Nb, Ni, Pb, Rb, S, Sb, Sc, Se, Sn, Sr, Th, Ti, Tl, V, W, Y and Zn provided that for some of these elements one does not get total recovery with HNO₃-digestion. This, nevertheless, supplies sufficient information for most concerns. Analytical problems were encountered for the following elements: U and Te concentrations in our samples were close to the blanks; P and Ta were highly variable within the sampling areas; B, Hf and Zr leached out of the glass of the digestion vessels; Hg is highly volatile.Field studies at three background sites in Switzerland, two on the northern side of the Alps and one in the southern Alps, showed higher burdens of element emissions in the latter, partly because of higher precipitation, and partly because of higher concentrations in the dust. An anthropogenic influence can be inferred for Ag, Bi, Cd, Cu, Hg, Mo, Pb, Sb, Te, W and Zn and probably also for As, P, S (with associated Se) and Sn.     

Biomonitoring in the forest zone of Ghana: the primary results obtained using neutron activation analysis and lichens

The first heavy metal deposition survey using biological indicators in the forest belt of Ghana was carried out in the year 2002–2003. The selected sampling areas included two mining centres, industrial areas and farming communities. Levels of ten chemical elements namely, Al, As, Cr, Fe, Hg, Mn, Sb, Th, Ti and V present in the lichens at high concentrations that are suspected to be resulting from anthropogenic activities were reported in these areas. The result shows that, the farming communities are relatively clean with the gold mining areas being the most polluted areas with respect to As, Sb and Cr. The industrial areas were found to be relatively polluted with Al, Fe and Ti.     

Characteristics of road dust from different sampling sites in northern Taiwan

Road dust contributes a large percentage of the atmosphere's suspended particles in Taiwan. Three road dust samples were collected from downtown, electrical park, and freeway tunnel areas. A mechanical sieve separated the road dust in the initial stage. Particles > 100 microm were 75%, 70%, and 60% (wt/wt), respectively, of the samples. Those particles < 37 microm were resuspended in another mixing chamber and then collected by a Moudi particle sampler. The largest mass fraction of resuspended road dust was in the range of 1-10 microm. Ultrafine particles (< 1 microm) composed 33.7, 17, and 7.4% of the particle samples (downtown, electrical park, and freeway tunnel, respectively). The road dust compositions were analyzed by inductively coupled plasma (ICP)-atomic emissions spectroscopy and ICP-mass spectrometry. The highest concentration fraction contained more aluminum (Al), iron (Fe), calcium (Ca), and potassium than other elements in the road dust particle samples. Additionally, the sulfur (S) content in the road dust from the electrical park and freeway tunnel areas was 2.1 and 3.4 times the downtown area sample, respectively. The sulfur originated from the vehicle and boiler oil combustion and industrial manufacturing processes. Furthermore, zinc (Zn) concentration in the tunnel dust was 2.6 times that of the downtown and electrical park samples, which can be attributed to vehicle tire wear and tear. Resuspended road dusts (< 10 microm) from the downtown and freeway tunnel areas were principally 2.5-10 microm Al, barium (Ba), Ca, copper (Cu), Fe, magnesium (Mg), sodium (Na), antimony (Sb), and Zn, whereas arsenic (As), chromium (Cr), and nickel (Ni) were predominant in the ultrafine particle samples (< 1 microm). Al, Ba, and Ca are the typical soil elements in coarse particles; and As, and Cr and Ni are the typical fingerprint of oil combustion and vehicle engine abrasion in ultrafine particles. There was a special characteristic of resuspension road dust at electrical park, that is, many elements, including As, Ba, Ca, cadmium, Cr, Cu, Fe, manganese (Mn), Ni, lead (Pb), S, vanadium (V), and Zn, were major in ultrafine particles. These elements should be attributed to the special manufacturing processes of electric products.     

Trace element accumulation by moss and lichen exposed in bags in the city of Naples (Italy)

This paper presents the results of a bioaccumulation study of trace elements in the Naples urban area based on the use of the moss Sphagnum capillifolium (Ehrh.) Hedw. and the lichen Pseudevernia furfuracea (L.) Zopf exposed in bags in 23 sites. Moss and lichen bags were exposed for 4 months starting from the beginning of July 1999. Bags gathering was carried out after 10 weeks of exposure, at the end of the dry season, and after 17 weeks, during the wet season. The elements Al, As, Ca, Cd, Cr, Co, Cu, Fe, K, Mg, Mn, Mo, Ni, Pb, Ti, V and Zn were analysed by inductively coupled plasma-mass spectrometry ICP-MS in both biomonitors. For the majority of the elements the total amounts found in S. capillifolium were higher than in P. furfuracea whether considering the whole period of exposure or the weekly uptake. It was observed that there was a much greater difference in metal accumulation by P. furfuracea between the dry and wet seasons compared with S. capillifolium. In the wet period, the lichen seems to accumulate a larger quantity of metals. With the exception of Mn, trace element concentrations did not appear to be significantly affected by the washing away of rainfall. K loss during exposure suggested cell membrane damage in both organisms. For P. furfuracea the K leakage was limited to the dry period of exposure. A clear distinction between "lithophilic" and "anthropogenic" elements was achieved by cluster analysis. Significant correlations were found among Fe-Cu-Cr-Ni, Pb-Cd-Co, V-Cr-Ni, Zn-Ni-Pb, suggesting a common source for each group of elements.     

Determination of major natural and anthropogenic source profiles for particulate matter and trace elements in Izmir, Turkey

Samples of PM10 and PM2.5 were collected from several natural and anthropogenic sources using in-stack cyclone, grab sampling/resuspension chamber and ambient air samplers. The chemical characterization of the samples was achieved containing Al, Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, V and Zn using an inductively coupled plasma-optical emission spectrometer (ICP-OES). The elemental fractions (weight percent by mass), standard deviations and uncertainties were reported. The elemental compositions of PM emitted from mineral industries and cement kiln were dominated by terrestrial elements, particularly Ca, whereas the profile of top-soil mainly contained Al and Ca. The profiles of industrial sources were generally typical for related ones; however, significant differences were obtained for some of them. Similarly, the profiles of fuel burning emissions have significant differences compared to profiles obtained all around the world.     

Characteristics of Road Dust from Different Sampling Sites in Northern Taiwan

Abstract

Road dust contributes a large percentage of the atmosphere’s suspended particles in Taiwan. Three road dust samples were collected from downtown, electrical park, and freeway tunnel areas. A mechanical sieve separated the road dust in the initial stage. Particles >100 μm were 75%, 70%, and 60% (wt/wt), respectively, of the samples. Those particles <37 μm were resuspended in another mixing chamber and then collected by a Moudi particle sampler. The largest mass fraction of resuspended road dust was in the range of 1–10 μm. Ultrafine particles (<1 μm) composed 33.7, 17, and 7.4% of the particle samples (downtown, electrical park, and freeway tunnel, respectively). The road dust compositions were analyzed by inductively coupled plasma (ICP)-atomic emissions spectroscopy and ICP-mass spectrometry. The highest concentration fraction contained more aluminum (Al), iron (Fe), calcium (Ca), and potassium than other elements in the road dust particle samples. Additionally, the sulfur (S) content in the road dust from the electrical park and freeway tunnel areas was 2.1 and 3.4 times the downtown area sample, respectively. The sulfur originated from the vehicle and boiler oil combustion and industrial manufacturing processes. Furthermore, zinc (Zn) concentration in the tunnel dust was 2.6 times that of the downtown and electrical park samples, which can be attributed to vehicle tire wear and tear. Resuspended road dusts (<10 μm) from the downtown and freeway tunnel areas were principally 2.5–10 μm Al, barium (Ba), Ca, copper (Cu), Fe, magnesium (Mg), sodium (Na), antimony (Sb), and Zn, whereas arsenic (As), chromium (Cr), and nickel (Ni) were predominant in the ultrafine particle samples (<1 μm). Al, Ba, and Ca are the typical soil elements in coarse particles; and As, and Cr and Ni are the typical fingerprint of oil combustion and vehicle engine abrasion in ultrafine particles. There was a special characteristic of resuspension road dust at electrical park, that is, many elements, including As, Ba, Ca, cadmium, Cr, Cu, Fe, manganese (Mn), Ni, lead (Pb), S, vanadium (V), and Zn, were major in ultrafine particles. These elements should be attributed to the special manufacturing processes of electric products.     

西湖沉积物中元素分布特征研究

分析测定了西湖沉积物（２０ｍ钻探样品）不同层次中Ｆｅ、Ａｌ、Ｃａ、Ｍｇ、Ｔｉ、Ｍｎ、Ｃｕ、Ｚｎ、Ｃｄ、Ｎｉ、Ｈｇ、Ｃｒ、Ａｓ、Ｃｏ、Ｖ等１５种元素的含量，并根据元素的分布特征探讨了西湖沉积物的形成发展及重金属污染状况。