Distribution, correlation, and source apportionment of selected metals in tannery effluents, related soils, and groundwater—a case study from Multan, Pakistan

The short-term responses of H₂O₂-depletion-related parameters in moss Hypnum plumaeforme to the combined stress induced by Pb and Ni were investigated. The results showed that the Pb and Ni stress induced dose-dependent accumulation of hydrogen peroxide (H₂O₂). The increase of peroxidase (POD) activity and decrease of ascorbate peroxidase (APX) activity were observed under the combined heavy metal application. The antioxidants, ascorbate (AsA) and proline content, increased significantly when the metals were applied together. The study indicated that the cell damage caused by Pb stress was higher than that caused by Ni stress, Pb and Ni had synergistic effect in inducing the oxidative stress in moss H. plumaeforme, especially under the combination of high concentration of Ni (0.1 and 1.0 mM) and Pb. Content of proline, H₂O₂ and the activity of POD, all showed a dose-dependent increase under Pb and Ni stress, suggesting their practical value as biomarkers in moss biomonitoring, especially in the case of light pollution caused by heavy metals without the changes in the appearance of mosses.     

Oxidative stress in Nile tilapia (Oreochromis niloticus) and armored catfish (Pterygoplichthys anisitsi) exposed to diesel oil

Considering that diesel oil is one of the most common aquatic contaminants, we compare the oxidative stress between two species of fish with different habitats (Pterygoplichthys anisitsi, benthic and Oreochromis niloticus, nektonic) exposed to diesel oil. Malondialdehyde concentrations (MDA) and the activities of ethoxyresorufin-O-deethylase (EROD), glutathione S-transferase (GST), catalase (CAT), superoxide dismutase (SOD), and glutathione peroxidase were all analyzed in the fishes' livers and gills after 2 and 7 days of exposure to different concentrations of diesel (0.1 and 0.5 mL/L). In the tilapia, MDA levels and the activities of EROD and GST activity in the liver, as well as MDA levels and the activities of GST and SOD in the gill had statistically significant differences between the treatments and between the times of exposure. For the catfish, the same occurred in the case of MDA, EROD, and SOD in the liver and in CAT and SOD in the gills. There were significant differences in the enzyme activity and lipid peroxidation between the species. Although the activity of most enzymes seemed to be more expressive and responsive to diesel in O. niloticus, diesel oil also caused significant effects on oxidative stress parameters in P. anisitsi, even though this species is benthic and thus has less access to insoluble fractions of diesel oil. Therefore, both species can be used as sentinel organisms in environmental biomonitoring of diesel contamination.     

Critical analysis of the potential of Ipomoea nil'Scarlet O'Hara' for ozone biomonitoring in the sub-tropics

This study aimed to analyze critically the potential of Ipomoea nil'Scarlet O'Hara' for O(3) biomonitoring in the sub-tropics. Four field experiments (one in each season of 2006) were carried out in a location of the city of S?o Paulo mainly polluted by O(3). Each experiment started with 50 plants, and lasted 28 days. Sub-lots of five plants were taken at intervals between three or four days long. Groups of four plants were also exposed in closed chambers to filtered air or to 40, 50 or 80 ppb of O(3) for three consecutive hours a day for six days. The percentage of leaf injury (interveinal chloroses and necroses), the concentrations of ascorbic acid (AA) and the activity of superoxide dismutase (SOD) and peroxidases (POD) were determined in the 5th, 6th and 7th oldest leaves on the main stem of the plants taken in all experiments. Visible injury occurred in the plants from all experiments. Seasonality in the antioxidant responses observed in plants grown under field conditions was associated with meteorological variables and ozone concentrations five days before leaf analyses. The highest levels of antioxidants occurred during the spring. The percentage of leaf injury was explained (R(2) = 0.97, p < 0.01) by the reduction in the levels of AA and activity of POD five days before the leaf analyses and by the reduction in the levels of particulate matter, and enhancement of temperature and global radiation 10 days before this same day. Although I. nil may be employed for qualitative O(3) biomonitoring, its efficiency for quantitative biomonitoring in the sub-tropics may be compromised, depending on how intense the oxidative power of the environment is.     

Analysis of selected biomonitors to evaluate the suitability for their complementary use in monitoring trace element atmospheric deposition

The biomonitoring properties of oak tree bark compared with the epiphytic moss Hypnum cupressiforme and the influence of the tree bark, as its growth substrate, on the content of heavy metals in moss were investigated. Samples of the epiphytic moss H. cupressiforme and oak tree bark (Quercus spp.) were collected in Eastern Romania at a total of 44 sampling sites. Parallel moss and bark samples were collected from the same sides of the trunk circumference. V, Cr, Ni, Cu, Zn, As, Mo, Cd, In, Tl, Sn, Pb, and Bi were determined by ICP-MS. Principal component analysis was used to identify possible sources of metals in bark and moss. Six factors explaining 87 % of the total variance in the data set were chosen. The main factors represent long-range atmospheric transport of elements (Zn, Cd, (Pb), Bi, (Mo), (Tl)), local emissions from industrial sources (As, Cr, Ni, V), road traffic (Pb, Zn) and agricultural activities (Cu, (Zn)). The element concentrations in moss and bark samples are of the same order of magnitude. For almost all the elements, higher concentrations were obtained in moss. Significant correlations between concentrations in moss and bark samples were obtained for 7 of the 13 elements: V, Ni, Cu, Zn, Cd, In, and Bi, all typical anthropogenic pollutants. The use of tree bark for monitoring purposes might be an alternative in areas where there is a scarcity of mosses.     

Comparison of two metal surveys by moss Tortula ruralis in Budapest, Hungary

Moss transplants of Tortula ruralis were used as active biomonitoring organisms as part of a monitoring study to assess the metals (Al, Cd, Cu, Cr, Fe, Ni, Pb, V and Zn) associated with ambient particles on mosses in Budapest, the capital town of Hungary. The moss samples were collected in a nature conservation area from a semi-arid sand grassland (Festucetum vaginatae danubiale), less than 1 month before transplantation. Moss cushions were exposed to pollution in Budapest during October–November 1993 and February–March 1994. In the study area, 16 sites were marked out as measuring sites, in accordance with the structure of the city. A similar stand was established in the Botanical Gardens of the Szent István University in Gödöll? as a control site. ICP-AES analysis of moss for metals showed the ability of Tortula ruralis to accumulate the metals under study. Control site showed lower impact in comparison to the other sites.     

Effects of coal spoil amendment on heavy metal accumulation and physiological aspects of ryegrass (<Emphasis Type="Italic">Lolium perenne</Emphasis> L.) growing in copper mine tailings

Copper mine tailings pose many threats to the surrounding environment and human health, and thus, their remediation is fundamental. Coal spoil is the waste by-product of coal mining and characterized by low levels of metals, high content of organic matter, and many essential microelements. This study was designed to evaluate the role of coal spoil on heavy uptake and physiological responses of Lolium perenne L. grown in copper mine tailings amended with coal spoil at rates of 0, 0.5, 1, 5, 10, and 20%. The results showed that applying coal spoil to copper mine tailings decreased the diethylenetriaminepentaacetic acid (DTPA)-extractable Cd, Cu, Pb, and Zn contents in tailings and reduced those metal contents in both roots and shoots of the plant. However, application of coal spoil increased the DTPA-extractable Cr concentration in tailings and also increased Cr uptake and accumulation by Lolium perenne L. The statistical analysis of physiological parameters indicated that chlorophyll and carotenoid increased at the lower amendments of coal spoil followed by a decrease compared to their respective controls. Protein content was enhanced at all the coal spoil amendments. When treated with coal spoil, the activities of superoxide dismutases (SOD), peroxidase (POD), and catalase (CAT) responded differently. CAT activity was inhibited, but POD activity was increased with increasing amendment ratio of coal spoil. SOD activity increased up to 1% coal spoil followed by a decrease. Overall, the addition of coal spoil decreased the oxidative stress in Lolium perenne L., reflected by the reduction in malondialdehyde (MDA) contents in the plant. It is concluded that coal spoil has the potential to stabilize most metals studied in copper mine tailings and ameliorate the harmful effects in Lolium perenne L. through changing the physiological attributes of the plant grown in copper mine tailings.     

Trace element biomonitoring using mosses in urban areas affected by mud volcanoes around Mt. Etna. The case of the Salinelle, Italy

Trace element impact was assessed using mosses in a densely inhabited area affected by mud volcanoes. Such volcanoes, locally called Salinelle, are phenomena that occur around Mt. Etna (Sicily, Italy) and are interpreted as the surface outflow of a hydrothermal system located below Mt. Etna, releasing sedimentary fluids (hydrocarbons and NaCl brines) along with magmatic gases (mainly CO(2) and He). To date, scarce data are available about the presence of trace elements, and no biomonitoring campaigns are reported about the cumulative effects of such emissions. In this study, concentrations of Al, As, Cd, Cr, Cu, Hg, Mn, Ni, Pb, V, and Zn were detected in the moss Bryum argenteum, in soil and water. Results showed that the trace element contribution of the Salinelle to the general pollution was significant for Al, Mn, Ni, and Zn. The comparison of trace concentrations in mosses from Salinelle and Etna showed that the mud volcanoes release a greater amount of Al and Mn, whereas similar values of Ni were found. Natural emissions of trace elements could be hazardous in human settlements, in particular, the Salinelle seem to play an important role in environmental pollution.     

Analysis of mosses and topsoils for detecting sources of heavy metal pollution: multivariate and enrichment factor analysis

In order to assess the contribution of emission sources to the pollution of areas remote from industrial facilities, a combined approach of enrichment factor analysis and multivariate statistics was used for detecting the origin of heavy metal pollution in the Zlatibor ecosystem, in Serbia. Samples of moss (Pleurozium schreberi, Hylocomium splendens, Scleropodium purum, Hypnum cupressiforme and Thuidum delicatulum) and of topsoil (0-5 cm) were collected in 2005. The concentrations of seven heavy metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) were determined in moss and soil samples by atomic absorption spectrometry. The results obtained by enrichment factor analysis and two multivariate statistical methods, principal component analysis and cluster analysis, enabled discrimination of the lithologic and anthropogenic sources of heavy metals in the mosses. Enrichment factors, calculated to evaluate the contribution to the metal content in moss from anthropogenic sources, revealed pollution of the investigated area by Cd and Pb, originating from long-range transport and fossil fuel burning.     

Cross-border response of mosses to heavy metal atmospheric deposition in Southeastern Bulgaria and European Turkey

First cross-border atmospheric pollution of 11 heavy metals and toxic elements assessed by Hypnum cupressiforme was reported for a part of Southeastern Europe (Southeastern Bulgaria and European Turkey). Moss monitoring technique followed the main requirements of European Moss Survey. Moss samples were collected in April 2006 both in Bulgaria and Turkey. Concentration of Al, As, Cd, Cr, Cu, Fe, Ni, Pb, Sb, V, and Zn were determined by ICP-AES. Interlaboratory parallel calibration (exchanged four moss samples from each country), standard reference moss materials (M2 and M3) results ensured the study. ANOVA showed no differences between measured results in both laboratories at the 99% confidence level. Principle Component Analyze proved two factors: F1 group of Al, As, Cd, Cr, Fe, Ni, and V and F2 of Cu, Pb, and Zn as main atmospheric pollutants. Results obtained showed approximately Cu and Pb high concentrations around Istanbul and Burgas and Zn pollution in Istanbul district. Arsenic cross-border atmospheric pollution in the study area of Southeastern Europe was found.     

Assessment of Atmospheric Deposition of Heavy Metals and Other Elements in Belgrade Using the Moss Biomonitoring Technique and Neutron Activation Analysis

This study aimed at assessing atmospheric deposition of heavy metals and other elements using the moss genera Brachythecium sp. (B. rutabulum and B. salebrosum) and Eurhynchium sp. (E. hians and E. striatum) collected in autumn 2004 in the urban area of Belgrade. The concentrations of 36 elements (Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, As, Se, Br, Rb, Sr, Mo, Sb, I, Cs, Ba, La, Ce, Sm, Tb, Dy, Hf, Ta, W, Hg, Th, U) were determined in moss and local topsoil samples by instrumental neutron activation analysis. The concentration of elements in moss positively correlated to those obtained for topsoil. High enrichment factors for As, Zn, Mo, Br, Sb, Se, Hg and Cl, calculated to continental crust composition, gave an evidence for anthropogenic impact on urban area, mainly due to intensive vehicular traffic and fossil fuel combustion. The concentration of elements in moss, characteristic for fossil fuel combustion, obtained in this study were substantially lower than in the previous investigation (2000) conducted in the area of Belgrade. The level of concentrations for V, Cr, Ni, and As in moss from this study correlated to those measured for neighboring countries, and were several times higher than the base-level data from low polluted areas. The level of accumulated elements in both investigated moss genera were similar and all studied species could be combined for biomonitoring purposes in urban areas.     

Biological monitoring of atmospheric trace metal deposition in North-Eastern Nigeria

The epiphytic moss Polytrichum juniperinum and the tree bark of Azardirachta indica were used to determine the atmospheric Cd, Cu, Pb, Mn, Fe, Ni and Zn levels in the North-East region of Nigeria. A good correlation exists between levels in the moss and the tree barks. The Pb, Zn and Fe levels in both sample types were higher than other metals in most sites. There was no significant difference in the levels of Cd, Cu, Ni and Mn recorded for inhabited and forest sites. The area derives its atmospheric metal contamination from vehicular, urban, industrial and agricultural sources.     

Heavy metal uptake and its effect on macronutrients, chlorophyll, protein, and peroxidase activity of Paspalum distichum grown on sludge-dosed soils

This study assessed the heavy metal (Cr, Mn, Ni, Cu, Zn, and Pb) uptake and its effect on biochemical parameters in Paspalum distichum, a wetland plant. Sludge collected from Bhalswa waste dump, New Delhi, was used as heavy metal source and dosed in different proportions viz. 20%, 40%, 60%, and 80% to the garden soil. The plants accumulated metals mostly in belowground organs. The metal accumulation followed the order: Cr>Mn>Cu>Zn>Ni>Pb. The range of heavy metal concentration in tissue of belowground organs after 180 days of growth was 1,778.65–4,288.01 ppm Cr, 828.11–1,360 ppm Mn, 236.52–330.07 ppm Ni, 155.79–282.35 ppm Cu, 27.05–91.16 ppm Zn, and 27.09–50.87 ppm Pb. The biochemical parameters viz. chlorophyll and protein contents and peroxidase (POD) activity exhibited no considerable adverse effect indicating the plants’ tolerance towards heavy metals. The high POD activity and synthesis of new protein bands at high sludge-dosed plants were also in support of this fact.     

Seasonal variation of oxidative stress biomarkers in clams Ruditapes decussatus sampled from Tunisian coastal areas

Seven (7) sites from to the Tunisian coastal area were monitored through four seasons using several oxidative stress biomarkers including lipid peroxidation. Catalase (CAT) specific activity was determined in clam Ruditapes decussatus digestive gland. Lipid peroxidation was assessed in the same tissues using malondialdehyde (MDA) concentration, neutral lipid (NL) and lipofuscin accumulation. Results show that catalase specific activity varies between sites and fluctuates in time. The highest CAT activities were recorded in sites from Bizerta Lagoon and sites neighbouring Sfax city. Malondialdehyde accumulation in digestive gland cells seems to be very pronounced in animals sampled in summer and autumn. Digestive gland sections of clams sampled from reported heavy metal polluted sites exhibited higher volume density of residual bodies. Our results showed that the neutral lipids and lipofuscin content in clam's digestive gland are more sensitive to general stress as compared to other biomarkers, and could be used successfully in clams as early warning tools in field biomonitoring programs.     

Comparison of leaching tests for the study of trace metals remobilisation in soils and sediments

Several leaching tests were applied and compared to study metal remobilisation on various unpolluted and contaminated soils and on several contaminated sediments. The trace elements considered were Cd, Cr, Cu, Ni, Pb and Zn, and leaching tests consisted of the application of reagents with contrasting characteristics and strengths in order to assess the information provided. An extraction with aqua regia permitted the estimation of the pseudo-total metal content in the sample. Mild extractants such as H2O, CaCl2 and NaNO3 showed low and similar leaching capacities. Acid (CH3COOH) and complexing (EDTA) agents were more effective in remobilising trace metals from soils and sediments. Cd and Zn showed similar extraction characteristics under both extractant solutions, whereas Cu and Pb were more sensitive to complexation, and Ni and Cr to acidification processes. Sequential chemical extractions provided additional information on the association of the trace elements with the different soil and sediment phases. Cd and Zn showed the highest mobility, Pb was associated to reducible solid phases, Cu and Ni to oxidisable phases, and Cr remained mostly in the residual fraction. The results obtained in this paper provided valuable information for choosing a leaching test, which is an instrument of environmental analysis for the estimation of trace metal mobility.     

Heavy metal deposition in moss samples from East and South Marmara Region, Turkey

A survey of atmospheric heavy metal deposition in the east and south Marmara region, Turkey was carried out in September 2004. For this purpose, moss samples (Hypnum cupressiforme) were collected in a systematic network of 125 sites. Concentrations of the elements (Al, B, Ba, Ca, Cd, Fe, Co, Cr, Cu, K, Li, Mn, Na, Ni, Pb, Sr, Mg, Ti, and Zn) in the moss were used as an indication of the level of air pollution in the region. Significant differences in heavy metal concentrations, especially for Pb, Cd, Cu, and Zn, were recorded in the moss samples collected around industrialized and heavily populated cities (Istanbul, Bursa, Band?rma, Kocaeli, Biga-?an) and in an abandoned lead-mining area (Bal?kesir-Balya). A map of the spatial distribution of each element in the region was plotted, and enrichment factors were calculated. VARIMAX principal component analysis was applied to the data obtained, and five different components were obtained. The results showed that Pb, Cu, Cd, and Zn derived from anthropogenic and industrial sources while other elements came mostly from natural sources.     

Changes in the heavy metal and nutrient contents of dried feather mosses during long-term storage

This study measured heavy metal and nutrient concentrations of two feather mosses during the periods of dry storage. Samples (Hylocomium splendens, Pleurozium schreberi) were collected in the nationwide moss surveys carried out on the permanent sample plots of the 8th Finnish National Forest Inventory in 1985–86, 1990, 1995 and 2000. A small amount of each moss sample was analyzed soon after collection, and the remainder was dried and stored at the Paljakka environmental specimen bank (ESB). The 108 stored samples from 27 plots were reanalyzed in 2008. Concentrations of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) and nutrients (Ca, K, Mg, P) were determined and compared for each survey year. Overall, Fe, Pb and Cr concentrations decreased, and Cu concentrations increased significantly during storage. The greatest decrease was observed in samples from plots where their initial concentrations were the highest. Changes in the concentrations of Cd, Ni and Zn were less pronounced. The loss of heavy metals is likely due to drying when cell membranes rupture and some of the surface material is lost. K, P and, to some extent, Mg concentrations increased during storage, whereas Ca did not change significantly. Nutrient increase is probably due to their movement from older to younger growths during the initial phase of drying. Ca is mostly bound to cell walls and is not easily released. Results emphasize the importance of establishing the intended use of a stored moss prior to sampling, in order to select and optimize an appropriate storage technique.     

Lipid peroxidation and antioxidant defense enzymes in Clarias gariepinus as useful biomarkers for monitoring exposure to polycyclic aromatic hydrocarbons

The toxicological evaluations of crude oil, xylene, toluene and benzene were carried out against juvenile stages of Clarias gariepinus. On the basis of LC(50) value, benzene (0.017 ml/l) was found to be the most toxic followed by xylene (0.086 ml/l), toluene (0.398 ml/l) and crude oil (2.219 ml/l) was the least toxic. The results of the lipid peroxidation assay showed that the level of malonaldehyde (MDA) in liver and gills of fish exposed to all the test chemicals increased significantly (P < 0.05) when compared to control. Measurement of activities of antioxidant enzymes, superoxide dismutase (SOD), catalase (CAT) and glutathione-S-transferase (GST) in liver and gill of fishes exposed to sublethal concentration of the test chemicals over a 28-day period was found to decrease significantly (P < 0.05) when compared to control. The observed reduction in the activities of antioxidant defense enzymes such as SOD, CAT and GST in conjunction with an increase in MDA levels in the gill and liver tissues of test animals exposed to aromatic hydrocarbon compounds were recommended as a good battery of biomarkers for early detection of pollution during biomonitoring programmes.     

Integrated survey of water pollution in the Suquía River basin (Córdoba, Argentina)

We report a combined two-year seasonal monitoring of Suquía River basin using both chemical parameters and biomarkers measured in Jenynsia multidentata, aiming to correlate external levels of contaminants with the response of oxidative stress biomarkers in this fish. Identified pollution sources correspond to city sewage as well as agricultural and small industry activities downstream from Córdoba city. Physicochemical parameters integrated into a water quality index (WQI) were measured in Suquía River during dry and wet seasons. Ag, Mn, Cu, Cr, Ni, Fe, Pb and Zn were also monitored in water and sediment samples. Biomarkers include detoxication and antioxidant enzymes: catalase (CAT), glutathione peroxidase (GPX), glutathione S-transferase (GST) and glutathione reductase (GR). Enzymes showed a pollution dependent response, with increased activities in fish collected close to the sewage exit and progressive drop further downstream, matching changes in the Water Quality index. The combined use of biomarkers with water quality parameters allowed both the identification of pollution sources and the evaluation of effects of contaminants on the aquatic biota.     

The role of chromatin damage in nickel-induced carcinogenesis. A review of recent developments

Over the last years, we have been testing a hypothesis that molecular mechanisms of nickel-induced carcinogenesis include interactions of this metal with major chromatin components; DNA, histones, and protamines. Our investigations using synthetic peptide models have resulted in identification of nickel-binding sites in core histones H3 and H2A and in protamine P2. These are: the internal -Cys110-AIH- motif in histone H3: the C-terminal-E121-SHHKAKGK "tail" motif in histone H2A; and the N-terminal RTH- motif in protamine P2. Ni(II) bound to the H3 and P2 motifs enhances oxidative DNA base damage by H2O2. In contrast, Ni(II) complex with the H2A "tail" is not redox active. However, at pH 7.4, it undergoes hydrolysis yielding a new complex, Ni(II)-SHHKAKGK, reactive with H2O2 and capable of mediating DNA oxidation. The "tail" cutting of H2A has also been observed in cells cultured with Ni(II). In Ni(II) complex with the protamine P2 peptides, H2O2 causes degradation of the metal-binding His3 and the distant Tyr8 residues. This site-specificity results from a long-range structuring effect of Ni(II) on its protamine ligand. In conclusion, Ni(II) binding to some chromatin proteins in somatic and sperm cells may result in oxidative and structural damage to the proteins and DNA. These effects may alter the fidelity of DNA replication and gene expression and thus facilitate carcinogenesis, including paternally-mediated cancer in the progeny.     

江蓠对水体重金属铅镍的蓄积及生物修复研究

以活体细基江篱繁枝变型(Gracilariatunuistipitata var)作为研究材料,以Pb、Ni重金属离子为污染因子,通过室内静态模拟实验,综合利用等离子发射光谱仪,超速离心机.差速离心机等实验手段研究在单一离子污染胁迫下,江蓠对Pb、Ni重金属离子的短期去除效果,各重金属离子在其体内蓄积效应,江蓠质外体、...