Evaluation of geochemical methods for discrimination of metal contamination in Antarctic marine sediments: a case study from Casey Station

Detecting anthropogenic metal contamination in regional surveys can be particularly difficult when there is a lack of pre-disturbance data, especially when trying to differentiate low to moderate levels of contamination from background values. Furthermore, comparisons with other regional studies are confounded by differing analytical methods used and variations in sediment properties such as grainsize. Several types of geochemical technique, including weak acid partial extraction, strong acid extractions and total digestion have been used. Attempts have been made to overcome the influence that grainsize has on chemical concentrations in heterogeneous environments by analysing the fines, typically the mud fraction (<63 microm), in an attempt to improve the detection of anthropogenic contamination. Here we compare a weak acid partial extraction using 1M HCl and total digestion methods for a regional survey of reference and impacted sites in Antarctica using both whole sediment (<2 mm) and mud (<63 microm) fractions. The 1M partial extraction on whole sediment (<2 mm) most closely distinguished weakly, or moderately, impacted sites from reference locations. It also identified small scale within-location spatial variation in metal contamination that the total digest did not detect. Compared with total digests or analysis of the <63 microm fraction alone, this method minimised the possibility of a Type II statistical error in the regional survey - that is, failing to identify a site as being contaminated when it has elevated metal concentrations. To allow inter-regional comparison of sediment chemistry data from elsewhere in Antarctica, and also more generally, we recommend a 1M HCl partial extraction on whole sediment (<2 mm).     

A study of metal and metalloid contaminant availability in Antarctic marine sediments

Previous studies of impacted sites near Casey Station, Antarctica, have revealed elevated concentrations of metals and metalloids, particularly Cd, Cu, Fe, Pb, Sn and Zn in marine sediments. However, attempts to understand the availability and mobility of contaminant elements have not provided a true understanding of speciation. The current work shows, for the first time, that sediments in Brown Bay, an embayment adjacent to the Thala Valley waste disposal site, have elevated concentrations of sulfide, well in excess of that required to bind contaminant metals such as Cd, Cu, Pb and Zn. Furthermore, sediment characterisation using the BCR sequential extraction scheme has shown metal partitioning consistent with sulfides being the controlling factor in metal availability, thus explaining the low porewater concentrations of these metals. The speciation of Sn in Brown Bay, however, is still unclear with the BCR sequential extraction scheme partitioning Sn predominantly into the residual fraction despite Sn being readily extracted by dilute HCl.     

The study of metal contamination in urban soils of Hong Kong using a GIS-based approach

The study of regional variations and the anthropogenic contamination by metals of soils is very important for environmental planning and monitoring in urban areas. An extensive survey was conducted in the highly urbanized Kowloon area (46.9 km(2)) of Hong Kong, using a systematic sampling strategy with a sampling density of 3-5 composite soil samples (0-15 cm) per km(2). Geochemical maps of 'total' metals (Cd, Cr, Cu, Ni, Pb and Zn) from strong acid extraction in the surface soils were produced based on geographical information system (GIS) technology. A significant spatial relationship was found for Ni, Cu, Pb and Zn in the soils using a GIS-based analysis, suggesting that these metal contaminants in the soils of the Kowloon area had common sources. Several hot-spot areas of metal contamination were identified from the composite metal geochemical map, mainly in the old industrial and residential areas. A further GIS analysis revealed that road junctions, major roads and industrial buildings were possible sources of heavy metals in the urban soils. The Pb isotope composition of the contaminated soils showed clear anthropogenic origins.     

Measuring bioavailability of polychlorinated biphenyls in soil to earthworms using selective supercritical fluid extraction

If the release mechanisms during selective chemical extraction of persistent organic pollutants (POP) mimic release mechanisms in natural systems during biological uptake, then a selective non-exhaustive extraction could give a quantitative measure of the bioavailable POP fraction. Supercritical fluid extraction (SFE) is suggested as a possible technique to estimate the amount of bioavailable polychlorinated biphenyls (PCBs) at contaminated sites and hence serve as a new tool in risk assessment. The uptake of PCBs by earthworm (Eisenia foetida) was investigated. PCB contaminated soil was pre-extracted with selective non-exhaustive SFE (50 degrees C, 350 bar, 1h), which removed on average 70% of the individual PCBs. Earthworms were placed in this pre-extracted soil, as well as in untreated soil. After 10 days, the PCB uptake by earthworms in the two systems was compared. The bioaccumulation factor (BAF) was 83% lower in the pre-extracted system than in the untreated system, demonstrating that SFE extracts primarily bioavailable contaminants. From the data, the bioavailable fraction could also be calculated to be 75%, which is very close to the 70% removed by SFE under the applied conditions. This suggests that the chemical methodology is capable of measuring the bioavailable fraction very accurately in this system.     

Washing as a remediation technology applicable in soils heavily polluted by mining-metallurgical activities

A permanent solution in order to remediate a heavily contaminated soil is washing it utilizing the appropriate reagents. The study presented in this paper deals with the washing of a soil highly polluted by mining and metallurgical activities. Pollution consists of slags, sulphur compound waste and various low grade lead condensates, all rich in heavy metals and metalloids (Pb, As, Cu, Zn, Mn and Fe). Soil was washed with deionized water, 6, 3, 2 and 1 M HCl, 6 M H(2)SO(4), 6 M HNO(3) and 0.1 M Na(2)EDTA. High extraction efficiency was achieved with respect to hydrochloric acid even at the lowest concentration; the solubility of pollutants in nitric acid was low, while sulphuric acid was proven to be problematic with respect to lead. Mobilization of metals and metalloids under DI water effect was minimal indicating that the elements fraction that is weakly bound to soil particles is insignificant. Furthermore, a kinetic study was undertaken, utilizing 1 M HCl and 0.1 M Na(2)EDTA. Results illustrated that 1 M HCl was more effective for intermediate mixing times (up to 4 h) while 0.1 M Na(2)EDTA was better applicable to short mixing times (<1 h) and low pH values (pH < 7.1). 1 M HCl was proven to be very effective for the removal of pollutants from contaminated soil but the high metal content of the resulting solution necessitates further treatment for the retention of metals.     

Influence of sediment acidification on the bioaccumulation of metals in Ruditapes philippinarum

Background, aim and scope

The influence of pH (range 6.5–8.5) on the uptake of Zn, Cd, Pb, Cu, Ni, Cr, Hg, and As by juveniles of the clam Ruditapes philippinarum was examined in order to understand whether variation in sediment pH has significant repercussions on metal bioaccumulation.

Materials and methods

Clams were exposed to sediments collected in three locations in the Gulf of Cadiz (Huelva, Guadalquivir and Bay of Cadiz) and to contaminated particles derived from an accidental mining spill in Spain.

Results

With a notable exception of metal Cd, the concentration of metals within clams significantly increased (p?<?0.1) when sediment pH was lowered by one or two units. Moreover, the magnitude of this effect was dependent on the type of sediment contamination.

Discussion

Lower pH increases metal solubility and reduces or invert the metal sorption of metals to sediments. Increases in free metal ions in water favors metal uptake by clams, hence pH is an important factor controlling the mobility of these metals within sediments and their subsequent bioaccumulation within biota. Although sediment-water exchange of Cd can increase with acidification, this excess may be counterbalanced by the presence of ligands in seawater preventing the uptake by organism. Besides chlorines, Cd has also an affinity with carbonates and other ligands present in sea water. These Cd-carbonate complexes may reduce the bioavailable to organisms.

Conclusions

These results highlight the potential implications of sediment acidification, either due to the storage excess of organic matter or to the forced capture of CO₂, on the increasing metal availability to benthic organisms.

Recommendations and perspectives

This kind of studies should be increased to address the influence of acidification in the behavior, bioavailability, toxicity, and risk assessment of contaminants associated with sediments either above sub-seabed geological formations in marine environments or in high enriched by organic matter in estuarine areas. Recently, the capture of CO₂ in marine environments has been approved and started; it is necessary to address the potential impacts associated with leakages or other events occurring during the procedure of injection and storage of CO2.     

Combined use of DGT and transplanted shrimp (Litopenaeus vannamei) to assess the bioavailable metals of complex contamination: implications for implementing bioavailability-based water quality criteria

The diffusive gradients in thin films (DGT) were field deployed alongside the shrimp Litopenaeus vannamei at seven sites with different levels of contamination to assess the potentially bioavailable and toxic fraction of metal contaminants. After 7 days of exposure, several antioxidant biomarkers were quantified in hepatopancreas of exposed shrimps, and tissue levels as well as the total, dissolved, and DGT-labile concentrations of metal contaminants were determined in the pooled site samples. The results showed that the caged shrimps had high tissue contaminant concentrations and significantly inhibited antioxidant responses at the more contaminated sites. DGT-labile metal concentrations provided better spatial resolution of differences in metal contamination when compared with traditional bottle sampling and transplanted shrimp. The total, dissolved, and DGT-labile metal fractions were used to evaluate the potential bioavailability of metal contaminants, comparing with metal accumulation and further linking to antioxidant biomarker responses in tissues of exposed shrimps. Regression analysis showed the significant correlations between DGT-Cu concentrations and tissue-Cu and activities of some biomarker responses in the shrimp hepatopancreas. This indicated that DGT-labile Cu concentrations provided the better prediction of produced biological effects and of the bioavailability than the total or dissolved concentrations. The study supports the use of methods combining transplanted organisms and passive sampling for assessing the chemical and ecotoxicological status of aqueous environments and demonstrates the capability of the DGT technique as a powerful tool for measuring the bioavailability-based water quality in variable coastal environments.     

Speciation of metals in contaminated sediments from Oskarshamn Harbor,Oskarshamn, Sweden

Bottom sediments in coastal regions have been considered the ultimate sink for a number of contaminants, e.g., toxic metals. In this current study, speciation of metals in contaminated sediments of Oskarshamn harbor in the southeast of Sweden was performed in order to evaluate metal contents and their potential mobility and bioavailability. Sediment speciation was carried out by the sequential extraction BCR procedure for As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn and the exchangeable (F1), reducible (F2), oxidizable (F3), and residual (R) fractions were determined. The results have shown that Zn and Cd were highly associated with the exchangeable fraction (F1) with 42–58 % and 43–46 %, respectively, of their total concentrations in the mobile phase. The assessment of sediment contamination on the basis of quality guidelines established by the Swedish Environmental Protection Agency (SEPA) and the Italian Ministry of Environment (Venice protocol for dredged sediments) has shown that sediments from Oskarshamn harbor are highly contaminated with toxic metals, especially Cu, Cd, Pb, Hg, As, and Zn posing potential ecological risks. Therefore, it is of crucial importance the implementation of adequate strategies to tackle contaminated sediments in coastal regions all over the world.     

Evaluation of the toxicity of two soils from Jales Mine (Portugal) using aquatic bioassays

Soil contamination can be one path for streams and groundwater contamination. As a complement of chemical analysis and total contaminants determination, bioassays can provide information on the bioavailable fraction of chemical compounds, focusing on the retention and habitat function of soils. In this study the evaluation of the toxicity of two soils from the abandoned Jales Mine (Portugal) regarded both functions. The buffer capacity of soils was tested with bioassays carried out using the cladoceran Daphnia magna and the marine bacteria Vibrio fischeri. The habitat function of soils was evaluated with the reproduction bioassay with the collembolan Folsomia candida. The Microtox solid-phase test was performed with V. fischeri using soil as test medium, and soil elutriates were extracted to perform the Microtox basic test, and an immobilization and reproduction bioassay with D. magna. The marine bacteria showed high sensitivity to the soil with low heavy metal content (JNC soil) and to JNC soil elutriates, while the soil with highest heavy metal content (JC soil) or soil elutriates exposure did not cause any toxic effect. In the bioassays with D. magna, organisms showed sensitivity to JNC and also to JC soil elutriates. Both mobilization and reproduction features were inhibited. The bioassay with F. candida did not reflect any influence of the contaminants on their reproduction. Although JNC soil presented lower heavy metal contents, elutriates showed different patterns of contamination when compared to JC soil and elutriates, which indicates different retention and buffer capacities between soils. Results obtained in this study underlined the sensitivity and importance of soil elutriate bioassays with aquatic organisms in the evaluation strategy in soil ERA processes.     

Use of semipermeable membrane devices (SPMDs)

Triolein-containing semipermeable membrane devices (SPMDs) were employed as passive samplers to provide data on the bioavailable fraction of organic, waterborne, organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs) in streams flowing through a highly polluted industrial area of Bitterfeld in Saxony-Anhalt, Germany. The contamination of the region with organic pollutants originates in wastewater effluents from the chemical industry, from over one-hundred years of lignite exploitation, and from chemical waste dumps. The main objective was to characterise time-integrated levels of dissolved contaminants, to use them for identification of spatial trends of contamination, and their relationship to potential pollution sources. SPMDs were deployed for 43 days in the summer of 1998 at four sampling sites. The total concentration of pollutants at sampling sites was found to range from a low of 0.8 microgram/SPMD to 25 micrograms/SPMD for PAHs, and from 0.4 microgram/SPMD to 22 micrograms/SPMD for OCPs, respectively. None of the selected PCB congeners was present at quantifiable levels at any sampling site. A point source of water pollution with OCPs and PAHs was identified in the river system considering the total contaminant concentrations and the distribution of individual compounds accumulated by SPMDs at different sampling sites. SPMD-data was also used to estimate average ambient water concentrations of the contaminants at each field site and compared with concentrations measured in bulk water extracts. The truly dissolved or bioavailable portion of contaminants at different sampling sites ranged from 4% to 86% for the PAHs, and from 8% to 18% for the OCPs included in the estimation. The fraction of individual compounds found in the freely dissolved form can be attributed to the range of their hydrophobicity. In comparison with liquid/liquid extraction of water samples, the SPMD method is more suitable for an assessment of the background concentrations of hydrophobic organic contaminants because of substantially lower method quantification limits. Moreover, contaminant residues sequestered by the SPMDs represent an estimation of the dissolved or readily bioavailable concentration of hydrophobic contaminants in water, which is not provided by most analytical approaches.     

Bottom sediments of the Arabian Gulf--III. Trace metal contents as indicators of pollution and implications for the effect and fate of the Kuwait oil slick

The trace metal contents of 71 core samples collected in 1992 from the bottom sediments of the Arabian Gulf are used to determine the regional distribution of concentration and pollution levels of these substances in the region. Chronic contamination was recorded in seven locations: the northwestern area (Fe), the northeastern area (Fe, V and Ni), the north-central area (V and Ni), the central area (Fe, Pb, V and Ni), the south-central area (Cu), the eastern area (Cu) and the southeastern area (Fe, V and Ni). Present-day contamination was identified in three locations only: the north-central area (V), the central area (Pb, V and Ni) and the southeastern area (Fe, V and Ni). Diversified natural and anthropogenic inputs may have provided the sources of this contamination. The V/Ni ratios of recent marine sediments cannot be used in identifying oil spillages or in oil-sediment correlation studies. Positive correlations are found between increasing trace metal concentration and decreasing carbonate content and grain size, verifying that adsorption onto muds is the primary mechanism of trace metal concentration in marine sediments. Correlations with TOC (total organic carbon) contents indicate that organic matter is a significant concentrator only in the case of Pb and Cu. With the exception of the Fe contamination in the northwest area due to river transport, all chronic and present-day trace metal concentrations are within the permissible natural background levels in the western offshore areas, including the two areas thought to be polluted by the Kuwait oil slick, thereby supporting the idea that airborne fallout from oil fires was deposited in a limited coastal area between Kuwait and Bahrain, and verifying that the oil slick had minimal effect on the state of pollution by trace metals in the Arabian Gulf.     

Field validation of a battery of biomarkers to assess sediment quality in Spanish ports

Two marine invertebrates, the crab Carcinus maenas and the clam Ruditapes philippinarum, were used as bioindicator species to assess contamination when exposed in situ to sediment from different sites from four Spanish ports Cadiz (SW Spain), Huelva (SW Spain), Bilbao (NE Spain) and Pasajes (NE Spain). In an attempt to determine sediments toxicity, a combination of exposure biomarkers was analyzed in both species: metallothionein-like-proteins (MTLPs), ethoxyresorufin O-deethylase (EROD), glutathione S-transferase activity (GST), glutathione peroxidase (GPX) and glutathione reductase (GR). In parallel, physical and chemical characterization of the different sediments was performed and biological responses related to the contaminants. Significant induction of MTLPs was observed when organisms were exposed to metal contaminated sediments (port of Huelva), and EROD and GPX activities after exposure to sediments containing organic compounds (port of Bilbao and Pasajes). No significant interspecies differences were observed in biomarker responses except for the GST and GR.     

Using Various Guidelines and Approaches for the Assessment of Marine Sediment Quality

The aim of the present study is to explore the implications of using different quality guidelines and approaches for marine sediment characterization. As a case study, the sediments of Souda Port, Crete, Greece, were examined in order to assess heavy metal contamination and to estimate anthropogenic contribution and potential adverse effects to aquatic environment, as well as to indicate feasible future management options. The concentration of six heavy metals (Co, Cr, Cu, Ni, Pb, and Zn) was determined and compared with different sediment quality guidelines (SQGs) and regional/national criteria established for dredged material characterization and management. In addition, the geo-accumulation index (I_geo) was calculated and the sediments toxicity and heavy metals bioavailability were determined. Based on the experimental data, it is deduced that Souda sediments are characterized as moderately polluted only in terms of Co, Ni, and Pb.     

Measurement of dynamic mobilization of trace metals in sediments using DGT and comparison with bioaccumulation in Chironomus riparius: first results of an experimental study

Sediments in aquatic ecosystems are often contaminated as a result of anthropogenic activities. Sediments and benthic organisms have been used to monitor trace metals contamination. However, due to the high variability of contaminant bioavailability, the attempt to link metal concentration in sediments and contamination of the organisms or ecotoxicological effect often lead to disappointing results. The technique of diffusive gradients in thin films (DGT) has been proposed as a relevant tool to study metal bioavailability, for example for accumulation in plants. In the present study, laboratory microcosm experiments were conducted with six contaminated sediments to compare metal accumulation in DGT and bioaccumulation in a chironomid (Chironomus riparius) for Cu, Cd and Pb . Metal accumulation in DGT was measured over time then modelled to determine two parameters of the dynamic response of the metals to DGT deployment: the size of the particulate labile pool and the kinetic of the solid-dissolved phase exchange. The mobility of metals was found metal and sediment dependent. A significant relationship between metal accumulated in DGT and bioaccumulated in chironomids was found for Cu and Pb. However, total metals in sediments were the best predictors of bioaccumulation. Nevertheless, the knowledge of the metals dynamic enhanced our ability to explain the different biological uptake observed in sediments of similar total metal concentrations.     

Variability of parameters measured during the resuspension of sediments with a particle entrainment simulator

The release of contaminants from sediments is an important problem facing environmental managers concerned with issues such as maintenance dredging, habitat restoration and dredge spoil placement. While there are laboratory methods to assess the remobilization of contaminants from resuspended sediments, little is known about how their operating characteristics influence a sediments response to resuspension. In this study, a particle entrainment simulator (PES) for resuspending sediments was evaluated by assessing variability among replicates and over operation time (12 h) for three estuarine sediments. These sediments varied in physical and chemical properties as well as the degree of metal contamination. Results showed that under identical resuspension conditions, there was low variability among sediment replicates. Sediment properties and the degree of metal contamination affected the magnitude and variation in water column parameters and contaminant release. Fine-grained sediments affected water column parameters, which stabilized over several hours of resuspension. While metal concentrations in the aqueous and particulate samples varied throughout operation, variation was highest for Cd and Ni. Compared to other methods used to evaluate the effects of sediment resuspension, the PES has operational advantages such as the ability to monitor water column conditions and resuspend sediment at specified energy levels. Overall, the PES provided reproducible conditions of resuspension effects among sediments varying in composition and contamination, demonstrating its value as a tool to evaluate contaminant mobility.     

Phagocytic response of macrophages from the pronephros of American plaice (Hipoglossoides platessoides) exposed to contaminated sediments from Baie des Anglais, Quebec.

Sediments of Baie des Anglais on the St. Lawrence estuary have a history of environmental contamination, but little information exists regarding their toxicity. The purpose of the present study was to determine the effects of contaminated Baie des Anglais sediments on American plaice (Hippoglossoides platessoides) immune function. Three sites in Baie des Anglais were selected which vary in proximity to local industries and in their sediment contaminant load. Sites 1 and 2 (within the bay) are the closest to shore and most heavily contaminated while sediments at Site 3, which is outside the bay, are the least contaminated. In the first experiment, American plaice were placed in cages at each site for three weeks and immune function was assessed by measuring the phagocytic activity of pronephric macrophages. At the time of sampling, plaice displayed pronephros cell immune response disturbances indicating that Site 1 and 2 were most toxic and Site 3 the least toxic. The results obtained for phagocytosis revealed that contaminants present in the sediments are bioavailable to fish, which came in contact with them and significantly affected their immune system. In the second experiment, sediments from the most toxic site, Site 1, were collected for a laboratory controlled experiment in which plaice were exposed for up to 3 months to these contaminated marine sediments, while the control group was exposed to relatively uncontaminated beach sand. At the end of the exposure period, plaice were transferred from contaminated sediment to beach sand and sampled one month later in order to determine if immune function had returned to control levels. The total number of macrophages decreased following three months of exposure, while the active macrophages had already decreased after the first month of exposure. Following the rehabilitation period a significant trend toward normal response was noted. Sediments from Baie des Anglais contain primarily less highly chlorinated PCBs and lower concentrations of the intermediate and highly chlorinated PCBs. The total concentration of PCBs (sum of 20 congeners) in the contaminated sediments was 1500 ng/g while in the beach sand, the levels were 13.6 ng/g dry weight. Only the low chlorinated PCB congeners were efficiently transferred from the sediments to the plaice liver. Together, these results suggest that the effect of chemical exposure on the phagocytosis of plaice macrophages may be reversible if the fish are returned to a non-contaminated habitat.     

Spatial and temporal variations of trace metals in bottom sediments of Peter the Great Bay, the Sea of Japan

New data on trace metal distribution in bottom sediments of Peter the Great Bay (the Sea of Japan) are presented. Much higher concentrations were detected near the most likely anthropogenic sources of trace metal inputs (waste water discharges from Vladivostok and Nakhodka, and the Vladivostok coastal landfill). Sediments in these contaminated areas were up to 700 ppm in Zn, 530 ppm in Pb, 7 ppm in Cd and 3 ppm in Hg. River runoff is of minor importance as a metal source in the investigated areas. The spatial distribution of trace metals outside the areas directly influenced by sewage discharges is regulated by natural processes such as sediment sorting by grain size. Based on radiometric dating of sediment cores, increases in the trace metal content of bottom sediments near Vladivostok begun in approximately 1945.     

Heavy metal in sediments of Ziya River in northern China: distribution,potential risks,and source apportionment

The concentration partitioning between the sediment particle and the interstitial water phase plays an important role in controlling the toxicity of heavy metals in aquatic systems. The aim of this study was to assess the sediment quality in a polluted area of the Ziya River, Northern China. The contamination potential and bioavailability of six metals were determined from the concentrations of total metals and the bioavailable fractions. The results showed that the concentrations of Cr, Cu, Ni, Zn, and Pb exceeded the probable effect concentration at several sites. The high geoaccumulation indices showed that the sediments were seriously contaminated by Cd. The ratio of acid-volatile sulfide (AVS) to simultaneously extracted metal (SEM) was higher than 1, which indicated that the availability of metals in sediments was low. The risk assessment of interstitial waters confirmed that there was little chance of release of metals associated with acid-volatile sulfide into the water column. Values of the interstitial water criteria toxicity unit indicated that none of the concentrations of the studied metals exceeded the corresponding water quality thresholds of the US Environmental Protection Agency. Positive matrix factorization showed that the major sources of metals were related to anthropogenic activities. Further, if assessments are based on total heavy metal concentrations, the toxicity of heavy metals in sediment may be overestimated.     

Heavy metal immobilization in soil near abandoned mines using eggshell waste and rapeseed residue

Heavy metal contamination of agricultural soils has received great concern due to potential risk to human health. Cadmium and Pb are largely released from abandoned or closed mines in Korea, resulting in soil contamination. The objective of this study was to evaluate the effects of eggshell waste in combination with the conventional nitrogen, phosphorous, and potassium fertilizer (also known as NPK fertilizer) or the rapeseed residue on immobilization of Cd and Pb in the rice paddy soil. Cadmium and Pb extractabilities were tested using two methods of (1) the toxicity characteristics leaching procedure (TCLP) and (2) the 0.1 M HCl extraction. With 5 % eggshell addition, the values of soil pH were increased from 6.33 and 6.51 to 8.15 and 8.04 in combination with NPK fertilizer and rapeseed residue, respectively, compared to no eggshell addition. The increase in soil pH may contribute to heavy metal immobilization by altering heavy metals into more stable in soils. Concentrations of TCLP-extracted Cd and Pb were reduced by up to 67.9 and 93.2 % by addition of 5 % eggshell compared to control. For 0.1 M HCl extraction method, the concentration of 0.1 M HCl-Cd in soils treated with NPK fertilizer and rapeseed residue was significantly reduced by up to 34.01 and 46.1 %, respectively, with 5 % eggshell addition compared to control. A decrease in acid phosphatase activity and an increase in alkaline phosphatase activity at high soil pH were also observed. Combined application of eggshell waste and rapeseed residue can be cost-effective and beneficial way to remediate the soil contaminated with heavy metals.     

Status of metal levels and their potential sources of contamination in Southeast Asian rivers

To assess the concentration and status of metal contaminants in four major Southeast Asian river systems, water were collected from the Tonle Sap–Bassac Rivers (Cambodia), Citarum River (Indonesia), lower Chao Phraya River (Thailand), and Saigon River (Vietnam) in both dry and wet seasons. The target elements were Be, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, Ba, Tl, and Pb and the concentrations exceeded the background metal concentrations by 1- to 88-fold. This distinctly indicates enrichment by human urban area activities. The results of a normalization technique used to distinguish natural from enriched metal concentrations confirmed contamination by Al, Cd, Co, Mn, Ni, Pb, and Zn. Cluster analysis revealed the probable source of metals contamination in most sampling sites on all rivers studied to be anthropogenic, including industrial, commercial, and residential activities. Stable lead isotopes analyses applied to track the sources and pathways of anthropogenic lead furthermore confirmed that anthropogenic sources of metal contaminated these rivers. Discharges of wastewater from both industrial and household activities were major contributors of Pb into the rivers. Non-point sources, especially road runoff and street dust, also contributed contamination from Pb and other metals.