Source origin of trace elements in PM from regional background,urban and industrial sites of Spain

Despite their significant role in source apportionment analysis, studies dedicated to the identification of tracer elements of emission sources of atmospheric particulate matter based on air quality data are relatively scarce. The studies describing tracer elements of specific sources currently available in the literature mostly focus on emissions from traffic or large-scale combustion processes (e.g. power plants), but not on specific industrial processes. Furthermore, marker elements are not usually determined at receptor sites, but during emission. In our study, trace element concentrations in PM₁₀ and PM_2.5 were determined at 33 monitoring stations in Spain throughout the period 1995–2006. Industrial emissions from different forms of metallurgy (steel, stainless steel, copper, zinc), ceramic and petrochemical industries were evaluated. Results obtained at sites with no significant industrial development allowed us to define usual concentration ranges for a number of trace elements in rural and urban background environments. At industrial and traffic hotspots, average trace metal concentrations were highest, exceeding rural background levels by even one order of magnitude in the cases of Cr, Mn, Cu, Zn, As, Sn, W, V, Ni, Cs and Pb. Steel production emissions were linked to high levels of Cr, Mn, Ni, Zn, Mo, Cd, Se and Sn (and probably Pb). Copper metallurgy areas showed high levels of As, Bi, Ga and Cu. Zinc metallurgy was characterised by high levels of Zn and Cd. Glazed ceramic production areas were linked to high levels of Zn, As, Se, Zr, Cs, Tl, Li, Co and Pb. High levels of Ni and V (in association) were tracers of petrochemical plants and/or fuel-oil combustion. At one site under the influence of heavy vessel traffic these elements could be considered tracers (although not exclusively) of shipping emissions. Levels of Zn–Ba and Cu–Sb were relatively high in urban areas when compared with industrialised regions due to tyre and brake abrasion, respectively.     

Metal concentrations in edible mushrooms following municipal sludge application on forest land

In the context of biosolids utilisation in forestry, effects of sludge application on mushroom metal concentration were studied in six sites of maritime pine forests in the South-West of France. Municipal sludge were applied at a rate of 6 T dry matter per hectare. Edible mushrooms were collected two years after sludge application. As, Cd, Cu, Hg, Pb, Se and Zn concentrations were determined. Results showed a high variability for trace element concentrations in mushrooms collected from control areas. No significant correlation was found between soil parameters (pH and trace elements concentrations) and mushroom trace element concentrations. Even if the concentration of trace metals increased in the soils, sludge application did not affect As, Cu, Se and Zn concentrations in carpophores but slightly increased Cd, Pb and Hg concentrations on some sites. This effect is dependent on sludge type and sites.     

Risk to breeding success of waterbirds by contaminants in Hong Kong: evidence from trace elements in eggs

Concentrations of 17 trace elements (As, Se, Rb, Sr, Ag, Sb, Cs, Tl, Pb, V, Cr, Mn, Co, Cu, Zn, Cd, and Hg) were determined in eggs of little egrets (Egretta garzetta), black-crowned night herons (Nycticorax nycticorax) and bridled terns (Sterna anaethetus) from northwestern and northeastern coastal areas of Hong Kong. Results indicated significant differences among the three species. Eggs of little egrets and black-crowned night herons appeared to be good bioindicators for monitoring selected elements (As, Pb, Zn Cr, Cu, and V) due to consistent correlations between metal concentrations in eggs and those in coastal marine sediments. Based on limited toxicological information, the predicted no effect concentrations (PNECs) of Hg and Se in the bird eggs were estimated as 0.5 to 1.8 and 0.90 to 1.45 mug g(-1), dry wt., respectively. Hazard quotients (HQs) indicated that Hg and Se might pose some risk to certain waterbirds in Hong Kong.     

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...     

Trace elements and butyltins in a Dall's porpoise (Phocoenoides dalli) from the Sanriku coast of Japan

Concentrations and body burdens of 14 trace elements (Hg, Cr, Mn, Co, Cu, Zn, Sr, Ag, Cd, V, Se, Pb, Mo, and Fe) and butyltins (BTs) (tributyltin TBT, dibutyltin DBT, and monobutyltin MBT) were determined in various tissues of a mature male Dall's porpoise (Phocoenoides dalli) collected off the Sanriku coast of Japan. Selective accumulation in this porpoise was observed for Hg, Mn, Cu, Ag, Mo, Fe, and total BTs (TBT, DBT, and MBT) in the liver, Cd in the kidney, Zn, Sr, V, Pb, and Co in the bone, and Se in the skin. In contrast, Cr concentrations in all tissues were similar. This distribution pattern in this mature porpoise was in general agreement with the accumulation characteristics of trace elements and butyltins reported for other marine mammals. The whole body of the porpoise contained approximately 62 g Fe, 8.8 g Zn, 4.0 g Sr, 0.6g Se, 0.41 g Cu, 0.19 g Hg, 0.17 g Cd, 0.16 g Mn, 0.05 g Cr, 0.009 g Ag, 0.008 g Mo, 0.005 g Pb, 0.004 g Co, and 0.7 mg of BTs (0.4 mg TBT, 0.2 mg DBT, and 0.1 mg MBT). Metabolism of TBT to its breakdown products of this porpoise seems to be limited, since TBT still accounted for about half of the total burden of BTs. As in the cases of Hg, Mn, Cu, Se, and Fe, the muscle was the most important reservoir (43%) for the whole body burden of total BTs, 80% of which was TBT, and thus muscle played a crucial role in the higher body composition of TBT in this Dall's porpoise.     

Trace elements in major solid-pesticides used in the Gaza Strip

This study describes the purity of pesticides used in Gaza in terms of trace elements. A semi-quantitative EMMA-XRF technique and quantitative ICP/OES was used to determine the concentrations of Al, As, Ba, Br, Ca, Cd, Co, Cr, Cu, Fe, K, Mn, Ni, Pb, Rb, Sc, Se, Sr, Ti and Zn in 50 of the most commonly used solid pesticides collected from the five central shops in the Gaza Strip. The results revealed that the pesticides contain considerable amounts of trace elements and do not comply with the expected-theoretical structure of each species. Moreover, they do not reflect the actual constituents mentioned in the trade labels. Interviews with market owners and field surveys confirmed that the pesticides were not pure. In some cases they have been mixed in local markets with minor inorganic species without a scientific basis. They may also have been smuggled into Gaza with differing impurities. The results indicate that pesticides should be considered as a source of certain trace metals (particularly Cu, Mn and Zn) and other elements (Br, Sr and Ti), which may affect their mass balances in soil and groundwater as well as their plant uptake. Different scenarios and calculation models of the transport of trace elements in soil and groundwater of the Gaza Strip should include pesticides as an additional source.     

Fractionation and extractability of sulfur, iron and trace elements in sulfidic sediments

This study describes iron and sulfur fractionation, and the related extractability of selected trace elements (As, Cd, Cr, Cu, Ni, Pb and Zn) in estuarine sediments. The sediments were sulfidic, with moderately high concentrations of pore-water sulfide (200-600 micromol l(-1)) and acid-volatile sulfide (AVS; 9.9-129 micromol g(-1)). Pyrite-S concentrations increased with depth, with 63-251 micromol g(-1) at site W1 and 312-669 micromol g(-1) at site W2. The degree of sulfidisation was generally high (>80%), indicating that Fe may be limiting pyrite accumulation. The ratios of AVS to pyrite-S increased with sediment depth, as expected for the pyritisation of solid-phase AVS. Cadmium, Pb and Zn extractability in 1M HCl indicated that these elements are not significantly sequestered during pyritisation, whereas sequestration may be important for As, Cu and possibly Ni. Extractability trends for Cr suggest that diagenesis in sulfidic sediments may enhance Cr reactivity. Overall, replacement of AVS by pyrite during diagenesis may enhance the reactivity of Cd, Cr, Pb and Zn, whereas As, Cu and possibly Ni may be rendered less reactive.     

Comparison of trace element accumulation in Baikal seals (Pusa sibirica), Caspian seals (Pusa caspica) and northern fur seals (Callorhinus ursinus)

Concentrations of 18 trace elements (V, Cr, Mn, Co, Cu, Zn, Se, Rb, Sr, Zr, Mo, Ag, Cd, Sb, Cs, Hg, Tl and Pb) were determined in liver, kidney, muscle and hair of Baikal seals, Caspian seals and northern fur seals. All the three species showed the highest concentrations of Hg, V, Mn, Se and Ag in liver, Cd, Co and Tl in kidney, and Cs in muscle among the soft tissues examined. The highest burdens of Zn, Rb and Cs were observed in muscle, Mo and Ag in liver, and Sb and Pb in hair in all the three species. Concentrations of non-essential elements, Rb, Cd, Cs and Hg, showed significant positive correlations among liver, kidney and muscle, whereas correlation coefficients for essential elements, Mn, Co, Cu, Zn and Se, between the three tissues were generally low for all the species, suggesting that homeostasis controls the concentrations of essential elements but not the non-essential elements in the tissues of these animals. Significant age-dependent increase was found in the concentrations of V, Se and Ag in liver and Hg in liver and kidney of all the three species. Hair concentrations showed significant positive correlations with Zn levels in liver and kidney and Hg in muscle for Caspian seals, Hg in liver and kidney for Baikal seals, and Pb in liver for northern fur seals. Furthermore, regression analysis using the data in the present study and in the literature showed significant positive correlations between Hg levels in hair, and liver, kidney and muscle for various species of pinnipeds. These results indicate the possibility of using hair samples for monitoring these trace elements in pinnipeds.     

Heavy metals in coastal wetland sediments of the Pearl River Estuary, China

Sediment quality in coastal wetlands of the Pearl River Estuary was concerned since the wetlands were used for land reclamation, aquaculture and wildlife protection, and meanwhile served as one of the main ultimate sinks for large amount of heavy metals discharged from the rapidly developing Pearl River Delta. Total concentrations of heavy metal, such as Zn, Ni, Cr, Cu, Pb, and Cd, and their chemical speciation were investigated. Results showed that the sediments were significantly contaminated by Cd, Zn and Ni with concentration ranges of 2.79-4.65, 239.4-345.7 and 24.8-122.1mg/kg, respectively. A major portion (34.6-46.8%) of Pb, Cd, and Zn was strongly associated with exchangeable fractions, while Cu, Ni and Cr were predominantly associated with organic fractions, residual, and Fe-Mn oxide. Cd and Zn would be the main potential risk and the sediment quality is no longer meeting the demand of the current wetland utilization strategies.     

Species- and age-related variation in metal exposure and accumulation of two passerine bird species

We measured the concentration of several elements (arsenic [As], calcium [Ca], cadmium [Cd], copper [Cu], nickel [Ni], lead [Pb], selenium [Se] and zinc [Zn]) in adult and nestling pied flycatchers (Ficedula hypoleuca) and great tits (Parus major) at different distances to a Cu-Ni smelter in 2009. Feces of nestlings generally failed to correspond with internal element concentrations but reflected the pollution exposure, indicating an increased stress by removal of excess metals. The uptake of Cu and Ni were regulated, but As, Cd, Pb and Se accumulated in liver tissue. Pied flycatchers had generally higher element concentrations than great tits. The higher accumulation of As and Pb in pied flycatcher livers was explained by a more efficient absorption, whereas the higher Cd concentration was primarily due to different intake of food items. Age-related differences occurred between the two species, though both Cd and Se accumulated with age.     

Characteristics and impacts of trace elements in atmospheric deposition at a high-elevation site,southern China

To investigate the regional background trace element (TE) level in atmospheric deposition (dry and wet), TEs (Fe, Al, V, Cr, Mn, Ni, Cu, Zn, As, Se, Mo, Cd, Ba, and Pb) in 52 rainwater samples and 73 total suspended particles (TSP) samples collected in Mt. Lushan, Southern China, were analyzed using inductively coupled plasma-mass spectrometry (ICP-MS). The results showed that TEs in wet and dry deposition of the target area were significantly elevated compared within and outside China and the volume weight mean pH of rainwater was 4.43. The relative contributions of wet and dry depositions of TEs vary significantly among elements. The wet deposition fluxes of V, As, Cr, Se, Zn, and Cd exceeded considerably their dry deposition fluxes while dry deposition dominated the removal of pollution elements such as Mo, Cu, Ni, Mn, and Al. The summed dry deposition flux was four times higher than the summed wet deposition flux. Prediction results based on a simple accumulation model found that the content of seven toxic elements (Cr, Ni, Cu, Zn, As, Cd, and Pb) in soils could increase rapidly due to the impact of annual atmospheric deposition, and the increasing amounts of them reached 0.063, 0.012, 0.026, 0.459, 0.076, 0.004, and 0.145 mg kg^?1, respectively. In addition, the annual increasing rates ranged from 0.05% (Cr and Ni) to 2.08% (Cd). It was also predicted that atmospheric deposition induced the accumulation of Cr and Cd in surface soils. Cd was the critical element with the greatest potential ecological risk among all the elements in atmospheric deposition.     

Trace element contamination of Norwegian Lake sediments

Concentrations of Sb, Hg, Bi, Cd, Mo, As, Co, Ni, Cr, Cu, V, Pb and Zn in surface and preindustrial sediments from 210 lakes in Norway were used for studying modern atmospheric depositions of these elements. Surface sediments had considerably higher concentrations of Sb, Hg, Bi, Cd, As, Pb than preindustrial sediments. The differences decreased with latitude and altitude. A multivariate analysis including the trace elements and the major constituents (organic matter, Si, Al, Fe and Mn) of surface sediments suggested the following relationships: Sb, Hg, Bi, As, and Pb formed a group with strong associations to organic matter. Ni, Cr and Cu formed a second group, weakly associated to the inorganic sediment fraction (Si and Al). Zn and Cd formed a third group with weak associations to organic matter. Co was associated to Mn, whereas Mo and V showed no important covariations with any other trace elements or major components.     

Specific accumulation of 20 trace elements in great cormorants (Phalacrocorax carbo) from Japan

This study is to elucidate the specific accumulation of 20 trace elements in tissues/organs of great cormorants from two different colonies (Lake Biwa and Mie) in Japan. In the body distribution of trace elements, some elements revealed tissue-specific accumulation such as most of the burden of Mo, Ag and Cd in liver, Tl and Cd in kidney, Cu, Rb and Cs in muscle, and V, Sr and Ba in bone. Gender-related variation was not observed in both populations for most of the trace elements, except for higher hepatic Sr in males from Lake Biwa. Hepatic V, muscular Hg and Tl, and Cd in liver, kidney and muscle increased with growth. Comparison of trace element levels in tissues between the two colonies showed that Cr, Rb, Sr, Cd, Cs, Ba and Tl levels were higher in Lake Biwa than in Mie, whereas Zn, Co and Hg in Mie samples were greater than Lake Biwa. Variations of elemental levels in stomach contents also showed similar patterns, thus, showing that dietary sources tended to be the main factor for these regional variations. Toxic Hg and Cd concentrations in the liver of cormorants from the two colonies were lower than those from other areas, implying relatively low exposure to these metals in the present study sites. Concentrations of V, Co, Ag, Cd, Cs, Hg, Tl, Pb and Bi in liver remained more or less at the same level between 1993 and 2003, while hepatic Cr, Mn, Cu, Zn, Se, Rb, Sr and Ba showed apparent decrease, which might be related to the biological factors.     

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。     

Topsoil (0-5 cm) composition in eight arctic catchments in northern Europe (Finland, Norway and Russia)

Frozen topsoil samples (0-5 cm) were collected during March/April 1994 in eight Arctic catchments in northern Europe (four in Russia, three in Finland, one in Norway), at different distances and in different wind directions from the emissions of the Russian mining, roasting and smelting industry on the Kola Peninsula. Between 14 and 25 sites were sampled in each of the eight catchments ranging in size from 12 to 35 km2. Results show that close to the smelters in Monchegorsk and Nikel, topsoil is clearly enriched in Ag, As, Bi, Cd, Co, Cr, Cu, Fe, Ni, Pb, Sb, Se, Te and V. Cu and Ni median contents in topsoils collected close to Monchegorsk are about 600 times higher than in the Finnish catchments. The effect of open-cast mining and waste dumps of alkaline rocks from the nephelinite industry near Kirovsk can be seen in the elevated contents of Al, Ba, K, La, Mn, Na, Sr, Ti, Y and Zn in topsoil collected in a nearby catchment. For many elements, however, variations observed in single catchments are as great as the total regional variation. Several elements (e.g. Cd, Hg, Cu, Ni, Pb, S, Zn) show strong positive correlation between the organic content of the sample and the element content observed. Thus it is necessary to determine the organic content of the samples and correct the element levels when using depth-related soil samples (here, the 0-5 cm topsoil layer) for regional mapping.     

Accumulation of potentially toxic elements in plants and their transfer to human food chain.

Contaminated soils can be a source for crop plants of such elements like As, Cd, Cr, Cu, Ni, Pb, and Zn. The excessive transfer of As, Cu, Ni, and Zn to the food chain is controlled by a "soil-plant barrier"; however, for some elements, including Cd, the soil-plant barrier fails. The level of Cd ingested by average person in USA is about 12 micrograms/day, which is relatively low comparing to Risk Reference Dose (70 micrograms Cd/day) established by USEPA. Food of plant origin is a main source of Cd intake by modern society. Fish and shellfish may be a dominant dietary sources of Hg for some human populations. About half of human Pb intake is through food, of which more than half originates from plants. Dietary intake of Cd and Pb may be increased by application of sludges on cropland with already high levels of these metals. Soils amended with sludges in the USA will be permitted (by USEPA-503 regulations) to accumulate Cr, Cd, Cu, Pb, Hg, Ni, and Se, and Zn to levels from 10 to 100 times the present baseline concentrations. These levels are very permissive by international standards. Because of the limited supply of toxicity data obtained from metals applied in sewage sludge, predictions as to the new regulations will protect crop plants from metal toxicities, and food chain from contamination, are difficult to make.     

Reconstructing temporal trends in heavy metal deposition: assessing the value of herbarium moss samples

The use of the herbarium moss archive for investigating past atmospheric deposition of Ni, Cu, Zn, As, Cd and Pb was evaluated. Moss samples from five UK regions collected over 150 years were analysed for 26 elements using ICP-MS. Principal components analysis identified soil as a significant source of Ni and As and atmospheric deposition as the main source of Pb and Cu. Sources of Zn and Cd concentrations were identified to be at least partly atmospheric, but require further investigation. Temporal and spatial trends in metal concentrations in herbarium mosses showed that the highest Pb and Cu levels are found in Northern England in the late 19th century. Metal concentrations in herbarium moss samples were consistently higher than those in mosses collected from the field in 2000. Herbarium moss samples are concluded to be a useful resource to contribute to reconstructing trends in Pb and Cu deposition, but not, without further analysis, for Cd, Zn, As and Ni.     

Anthropogenic metal enrichment of snow and soil in north-eastern European Russia

Trace metal composition of winter snowpack, snow-melt filter residues and top-soil samples were determined along three transects through industrial towns in the Usa basin, North-East Russia: Inta, Usinsk and Vorkuta. Snow was analysed for Ag, Al, As, Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr and Zn using ICP-MS (Ca and K by F-AAS for Vorkuta only), pH and acidity/alkalinity. Filter residues were analysed for: Al, Ba, Ca, Cd, Cu, K, Mg, Mn, Ni, Pb, Sr and Zn using F-AAS and GF-AAS; top-soil samples were analysed for Ba, Cu, Mg, Mn, Na, Ni, Pb, Sr, Zn using F-AAS. Results indicate elevated concentrations of elements associated with alkaline combustion ash around the coal mining towns of Vorkuta and Inta. There is little evidence of deposition around the gas and oil town of Usinsk. Atmospheric deposition in the vicinity of Vorkuta, and to a lesser extent Inta, added significantly to the soil contaminant loading as a result of ash fallout. Acid deposition was associated with pristine areas whereas alkaline combustion ash near to emission sources more than compensated for the acidity caused by SO2.     

Use of mosses (Hylocomium splendens and Pleurozium schreberi) as biomonitors of heavy metal deposition: from relative to absolute deposition values

Concentrations of 48 elements in the ground growing mosses Hylocomium splendens and Pleurozium schreberi have been compared with wet deposition data for the same elements at 13 Norwegian sites. Significant positive correlations were found for V, Fe, Co, As, Y, Mo, Cd, Sb, Ce, Sm, Er, Tl and Pb in Hylocomium splendens, and for Mg, V, Fe, Co, As, Se, Y, Mo, Cd, Sb, Tl and Pb in Pleurozium schreberi. Regression equations for transforming moss concentration data to absolute deposition rates have been calculated for those of the above elements which are of interest from a pollution point of view. The concentration levels of Li, Be, Mg, Ca, Zn, Ge, As, Se, Sr, Y, Zr, Sn, Cs, Ba, La, Ce, Pr, Nd, Sm, Ho, Yb, Hf, Ta and U were similar in the two moss species. Hylocomium splendens had highest concentrations of Cr, Fe, Co, Ni, Cu, Ga, Nb, Mo, Sb, Eu, Gd, Tb, Dy, Er, Tm, Lu, W, Tl, Pb and Th, whereas V, Mn, Rb and Cd were highest in Pleurozium schreberi. No variations were observed in the concentrations of the studied elements during the sampling season.