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.     

Determination of cadmium, zinc, copper, chromium and arsenic in crude oil cargoes

One of the sources of trace heavy metal elements in air is emission by the oil industry, either directly through stack emissions from refineries or indirectly from emissions of combustion of hydrocarbons. Emission estimates are based mainly on the trace metal content of the crude oil processed. From a literature study carried out at the beginning of the 1990s it became clear that data on the trace metal content of crudes were scarce and showed a very large scatter. For this reason a measurement programme to assess the occurrence and concentrations of a number of trace metals, i.e. Cadmium (Cd), Zinc (Zn), Copper (Cu), Chromium (Cr), and arsenic (As), in crudes which are regularly processed in the Netherlands, was set up. By drafting strict sampling protocols and by constructing a special sampling device, as many as possible of the additional contamination sources were avoided. The study suggests that sample contamination may explain a significant amount of the scatter and some of the high concentrations reported in the literature for certain metals. The measured variation in the concentrations of Cd, Zn, and Cu is thought to be due to associated water and/or sediment particles from the producing wells or that picked up during transport. The greater consistency in our measurements for Cr and As suggests that these metals are predominantly associated with the hydrocarbon matrix. Based on the results of this work, it can be concluded that emissions of Cd, Zn, Cu, Cr, and As by the oil industry in the Netherlands are most probably significantly lower than hitherto assumed.     

Evidence of excessive releases of metals from primitive e-waste processing in Guiyu, China

Guiyu, China is infamous for its involvement in primitive e-waste processing and recycling activities. Freshwater samples were collected in and outside of Guiyu for dissolved metal analysis. It was found that dissolved metal concentrations were higher in Lianjiang and Nanyang River within Guiyu than the reservoir outside of Guiyu. Lianjiang was enriched with dissolved As, Cr, Li, Mo, Sb and Se, while Nanyang River had elevated dissolved Ag, Be, Cd, Co, Cu, Ni, Pb and Zn. Temporal distributions of the metals suggested recent discharges of metals attributable to a strong acid leaching operation of e-waste, where dissolved Ag, Cd, Cu and Ni (0.344+/-0.014, 0.547+/-0.074, 87.6+/-3.0 and 93.0+/-1.4 microg/L, respectively) were significantly elevated. Pb isotopic composition of dissolved Pb confirmed that more than one non-indigenous Pb were present in Lianjiang and Nanyang River. In summary, it was evident that the riverine environment of Guiyu was heavily impacted by e-waste related activities.     

Occurrence of platinum and additional traffic related heavy metals in sediments and biota

Non-point sources play an important role in metal emissions into surface waters. One of the most important non-point sources is automobile traffic. Recent studies determining traffic related heavy metals in surface waters have concentrated mainly on worst case scenarios by analyzing heavy metal loads in waters and sediments close to storm-water overflow inlets. The present study aims at identifying traffic related heavy metals in moderately polluted sites, as they occur in highly urbanized regions. Therefore, the concentrations of eight traffic related metals (Pt, Sb, Mo, Cd, Pb, Cu, Cr and Zn) were determined in sediment and crustacean samples from eight different aquatic habitats in the Ruhr district, Germany. Traffic related heavy metals could be identified in sediment and biota samples as a combination of heavy metals (Pt, Sb, Cd, Pb for sediments and Pt and Sb for crustacean samples). Pt concentrations received special attention due to the relatively recent occurrence of anthropogenically emitted Pt in the environment. At six sampling sites, Pt was detected in sediment and/or biota samples. The uptake of Pt compared to other traffic related heavy metals by Asellus aquaticus and Gammarus pulex is relatively high and can be compared with the uptake rates of essential metals like Zn.     

Evaluating health risks posed by heavy metals to humans consuming blood cockles (<Emphasis Type="Italic">Anadara granosa</Emphasis>) from the Upper Gulf of Thailand

There is global concern about heavy metal contamination in the environment. Adverse health effects can be caused by heavy metals in contaminated food and water. Therefore, environmental monitoring studies and risk assessments should be conducted periodically. In this study, we measured levels of Cd, Cr, Cu, Hg, Mn, Ni, Pb, and Zn in blood cockles (Anadara granosa) collected from three locations in the Upper Gulf of Thailand. Hazard quotients and hazard indices were calculated to evaluate the health risks posed by heavy metals in consumed blood cockles. Heavy metal concentrations in all of the blood cockle samples were lower than the relevant food standards. The hazard quotients and hazard indices were <1 in all three sampling areas, indicating that adverse health effects were not likely to be caused by exposure to heavy metals in blood cockles over a human lifetime.     

Relationship between heavy metals concentrations in egret species,their environment and food chain differences from two Headworks of Pakistan

Concentration of ten metals (Cd, Cr, Co, Cu, Fe, Li, Mn, Ni, Pb and Zn) were analyzed in the egg contents, prey and soil samples of little egret (Egretta garzetta) and cattle egret (Bubulcus ibis) from two Headworks to determine habitat and species-specific differences; to assess the importance of prey and habitat contamination as an exposure source for heavy metals. Concentration of Cu, Mn, Cr and Pb in egg contents, Fe, Co, Cu, Mn, Zn in prey and Fe, Co, Cu, Ni, Li in surface soils were significantly different (P < 0.05). Mean metal concentrations of Cr, Pb and Cd were relatively higher in little egret whereas Cu and Mn were higher in the egg contents of cattle egret. The mean concentrations of Cu, Mn and Zn were higher in prey samples of cattle egrets and Cr, Cd and Pb in prey samples of little egrets. In soil samples collected from little egret heronries metal concentrations were higher except Cu and Ni. Correlation Analysis and Hierarchical Agglomerative Cluster Analysis (HACA) identified relatively similar associations of metals and their source identification. Metals such as Fe, Cu, Mn, and Li were related with geochemical origin from parent rock material as well as anthropogenic input whereas Cr, Cd, Pb, Ni, Co and Zn were associated mostly with anthropogenic activities. The study suggested that eggs are useful bio-monitor of local heavy metal contamination.     

Spatial Distribution Patterns,Sources of Heavy Metals,and Relation to Ecological Risk of Surface Sediments of the Cyprus Northern Shelf (Eastern Mediterranean)

In this study, the spatial distribution of metals and the sources of metal pollution were investigated along the Northern Shelf of Cyprus (Mediterranean Sea). The concentrations of heavy metals and organic matter were measured in sediments collected from the Gemi Konagi, Girne, and Gazi Magusa areas. Measured metal values were compared with Mediterranean background concentrations. Cu and Zn concentrations at the Gemi Konagi area and all of the Cr values were higher than Mediterranean backgrounds. The metal levels were evaluated by the enrichment factor (EF), contamination factor (C_f) and degree of contamination (C_d). EF results indicated that heavy metal sources were probably originated from natural processes and mining activities. The C_f values of Hg indicated low contamination. The C_d (degree of contamination) values for all heavy metals also showed a low degree of contamination at the study area. Metal levels were also compared with the numerical Sediment Quality Guidelines (SQG) for an environmental risk assessment. Results showed that sediments were classified as heavily polluted by Cu and moderately polluted by Zn at Gemi Konagi and heavily polluted by Cr and Ni contamination at all sampling areas per the SQG.     

Influences of dissolved and colloidal organic carbon on the uptake of Ag, Cd, and Cr by the marine mussel Perna viridis

The cross-flow ultrafiltration and radiotracer techniques were used to study the influences of natural dissolved organic carbon (DOC) and colloidal organic carbon (COC) on the bioavailability of Ag, Cd, and Cr to the green mussel Perna viridis. We examined the uptake of these metals by the mussels at different concentrations of DOC and COC from different origins (estuarine, coastal, and diatom decomposed). Using the DOC originating from the decomposed diatom (Thalassiosira pseudonana), we demonstrated that Cd and Cr uptake, quantified by the concentration factor (DCF), increased linearly with increasing DOC concentration. There was, however, no consistent influence of natural DOC concentration on the metal uptake when the DOC was obtained from different sources of seawater (coastal and estuarine). The influences of COC on metal bioavailability were metal-specific and dependent on the geochemical properties of colloids and colloid-metal complexation. Cd uptake rate was not influenced by the COC concentrations. Uptake of diatom-decomposed colloidal Cr was enhanced by 3.4x, whereas the uptake of diatom-decomposed colloidal Ag was decreased by 8.2x compared with the uptake of low molecular weight Cr and Ag (<1 kDa). The uptake of diatom-decomposed colloidal Cr and Ag was generally lower than the uptake of metals bound with the same type of colloids for 2 days. Further aging of the colloid-metal binding reduced metal bioavailability to the mussels. In the presence of different sizes of colloidal particles where there was no major binding of colloids with the metals, metal uptake by the mussels was not influenced by different COC concentrations. Overall, our study suggests that although metal dissociation from colloids may be an important step for the uptake of colloidal metals, other mechanisms such as pinocytosis and co-transport may also be involved in the uptake of these metals, especially in aquatic environments with high DOC and COC concentrations.     

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.     

Metal accumulation in the greentail prawn, Metapenaeus bennettae, in Sydney and Port Hacking estuaries, Australia

Metal concentrations of the inshore greentail prawn, Metapenaeus bennettae, and surface sediments from locations within Sydney estuary and Port Hacking (Australia) were assessed for bioaccumulation and contamination. The current study aimed to assess metal concentrations in prawn tissue (tail muscle, exoskeleton, hepatopancreas and gills), relate whole body prawn tissue metal concentrations to sediment metal concentrations and animal size, as well as assess prawn consumption as a risk to human health. Metal concentrations were highest in sediment and prawns from contaminated locations (Iron Cove, Hen and Chicken Bay and Lane Cove) in Sydney estuary compared with the reference estuary (Port Hacking). Concentrations in sediments varied considerably between sites and between metals (As, Cd, Cr, Cu, Ni, Pb and Zn), and although concentrations exceeded Interim Sediment Quality Guideline-Low values, metals (As, Cd, Cr, Cu, Ni, Pb and Zn) were below Australian National Health and Medical Research Council human consumption guidelines in prawn tail muscle tissue. Metal concentrations in prawn tail muscle tissue were significantly different (p?≤?0.05) amongst locations for Pb, Zn and Cd, and metal concentrations were generally highest in gills tissue, followed by the hepatopancreas, exoskeleton and tail muscle. The exoskeleton contained the highest Sr concentration; the hepatopancreas contained the highest As, Cu and Mo concentrations; and the gills contained the highest Al, Cr, Fe and Pb concentrations. Concentrations of Pb, As and Sr were significantly different (p?≤?0.05) between size groups amongst locations.     

Metal mobility during in situ chemical oxidation of TCE by KMnO4

The potential for trace-metal contamination of aquifers as a side effect of In Situ Chemical Oxidation (ISCO) of chlorinated solvent contamination by KMnO(4) is investigated with column experiments. The experiments investigate metal mobility during in situ chemical oxidation of TCE by KMnO(4) under conditions where pH, flow rate, KMnO(4), TCE, and trace-metal concentrations were controlled. During ISCO, the injection of MnO(4) creates oxidizing conditions, and acidity released by the reactions causes a tendency toward low pH in aquifers. In order to evaluate the role of pH buffering on metal mobility, duplicate columns were constructed, one packed with pure silica sand, and one with a mixture of silica sand and calcite. Aqueous solutions of TCE and KMnO(4) (with 1 mg/L Cu, Pb, Zn, Mo, Ni, and Cr(VI)) were allowed to mix at the inlet to the columns. After the completion of the experiments, samples of Mn oxide were removed from the columns and analyzed by analytical scanning and transmission electron microscopy. In order to relate the results of the laboratory experiments to field settings, the analyses of Mn-oxide samples from the lab experiments were compared to samples of Mn oxide collected from a field-scale chemical-oxidation experiment that were also analyzed by analytical electron microscopy as well as time-of-flight secondary-ion mass spectroscopy. The pH ranged from 2.40 in the silica sand column to 6.25 in the calcite-containing column. The data indicate that aqueous Mo, Pb, Cu and Ni concentrations are attenuated almost completely within the columns. In contrast, Zn concentrations are not significantly attenuated and Cr(VI) is transported conservatively. The results indicate that within the range 2.40 to 6.25, metal mobility is not affected by pH. Comparison of analyses of Mn-oxide from the lab and field demonstrate that a variety of metals are sequestered from solution by Mn oxide.     

A comparative study on metal sorption by brown seaweed

This study compared the sorption of Ag, Cd, Co, Cd, Mn, Ni, Pb and Zn by a Ca-treated Sargassum biomass at pH 5.0, under low and high ionic strength (IS) conditions. The sorption isotherms of As [As(V)] and Cr [Cr(III) and Cr(VI)] were also determined at low IS. The isotherm data for the eight cationic metals and Cr(III) were well fitted by Langmuir equations. Generally, the maximum metal uptake (Umax) followed: Cr(III) > Pb approximately Cu > Ag approximately Zn approximately Cd > Ni approximately Mn approximately Co > Cr(VI) > As(V) at low IS and Pb > Cu > Co > Mn approximately Cd > Zn approximately Ag > Ni at high IS. As(V) did not bind to the seaweed at pH 5.0. The results indicated that sorption of Pb was not affected by the increasing IS, though the percentage of free Pb ions in the water was greatly reduced as predicted by the speciation model. High IS lowered Umax by 10-36% (except Co and Pb), and lowered the affinity constant of the metal by 33-91% for all cationic metals, as compared to low IS. Moreover, the removal efficiency of the cationic metals and Cr decreased exponentially with initial metal concentrations and was lower at high IS. Ion-exchange was the mechanism responsible for the cationic metal sorption onto the seaweed, and Na ion interfered with the cationic metal binding through electrostatic interaction. In conclusion, this study showed the differential binding capacity of the Sargassm biomass for different metals and oxidation states and the differential effects of IS. According to the present results, Sargassum may be considered a good biosorbent for cationic metals (especially Pb) in both low and high-salt containing wastewater.     

Date palm (Phoenix dactylifera L.) leaves as biomonitors of atmospheric metal pollution in arid and semi-arid environments

The leaves of date palms were evaluated as a possible biomonitor of heavy metal contamination in Ma’an city, Jordan. Concentrations of (Fe), (Pb), (Zn), (Cu), (Ni), and (Cr) were determined in washed and unwashed leaves and soil samples collected from different sites with different degrees of metal contamination (urban, suburban, industrial, highway and rural sites); separate leaves were taken from outside the city to be used as a control sample. Samples collected from industrial sites were found to have high concentrations of all metals except those of Cu, Ni and Pb, which were found at high levels in the highway site samples which is associated with the road traffic. The difference between unwashed and washed samples showed that metal pollutants exist as contaminants, particularly Pb, Zn and Ni, which varied in concentration, depending on the source of the metal.     

Spatial variation of heavy metals in surface sediments of Hong Kong mangrove swamps

The degree of heavy metal contamination in the fine-grained (<63 microm) and sand-sized (2 mm-63 microm) fractions of surface sediments in 18 different mangrove swamps (144 random samples) in Hong Kong was examined. Higher concentrations of heavy metals were found in the fine-grained than the sand-sized fractions of the sediment; however, the differences between these two fractions became less significant when the swamp was more contaminated. The principal component analyses show that the 18 mangrove swamps, according to the median concentrations of total heavy metals, were clustered into four groups. The first group included three mangrove swamps in Deep Bay region which are seriously contaminated, with heavy metal concentrations in sediments around 80 microg g(-1) Cu, 240 microg g(-1) Zn, 40 microg g(-1) Cr, 30 microg g(-1) Ni, 3 microg g(-1) Cd and 80 microg g(-1) Pb. The second cluster, made up of another four swamps distributed in different geographical locations (two in Sai Kung district and two in Tolo region), also had elevated levels of Cu, Pb, Ni and Cr in the sediments. Field observation reveals that these seven stands received industrial, livestock and domestic sewage as well as pollution from mariculture activities, suggesting that anthropogenic input is the main source of heavy metal contamination in Hong Kong mangroves. The sediments from other mangrove swamps were relatively uncontaminated.     

Health risk assessment of heavy metals in soil-plant system amended with biogas slurry in Taihu basin,China

Biogas slurry is a product of anaerobic digestion of manure that has been widely used as a soil fertilizer. Although the use for soil fertilizer is a cost-effective solution, it has been found that repeated use of biogas slurry that contains high heavy metal contents can cause pollution to the soil-plant system and risk to human health. The objective of this study was to investigate effects of biogas slurry on the soil-plant system and the human health. We analyzed the heavy metal concentrations (including As, Pb, Cu, Zn, Cr and Cd) in 106 soil samples and 58 plant samples in a farmland amended with biogas slurry in Taihu basin, China. Based on the test results, we assessed the potential human health risk when biogas slurry containing heavy metals was used as a soil fertilizer. The test results indicated that the Cd and Pb concentrations in soils exceeded the contamination limits and Cd exhibited the highest soil-to-root migration potential. Among the 11 plants analyzed, Kalimeris indica had the highest heavy metal absorption capacity. The leafy vegetables showed higher uptake of heavy metals than non-leafy vegetables. The non-carcinogenic risks mainly resulted from As, Pb, Cd, Cu and Zn through plant ingestion exposure. The integrated carcinogenic risks were associated with Cr, As and Cd in which Cr showed the highest risk while Cd showed the lowest risk. Among all the heavy metals analyzed, As and Cd appeared to have a lifetime health threat, which thus should be attenuated during production of biogas slurry to mitigate the heavy metal contamination.     

Probing the distribution and contamination levels of 10 trace metal/metalloids in soils near a Pb/Zn smelter in Middle China

The horizontal and vertical distribution patterns and contamination status of ten trace metal/metalloids (Ag, Bi, Co, Cr, Ge, In, Ni, Sb, Sn, Tl) in soils around one of the largest Chinese Pb–Zn smelter in Zhuzhou City, Central China, were revealed. Different soil samples were collected from 11 areas, including ten agricultural areas and one city park area, with a total of 83 surface soil samples and six soil cores obtained. Trace metal/metalloids were determined by inductively coupled plasma–mass spectrometry after digestion by an acid mixture of HF and HNO₃. The results showed that Ag, Bi, In, Sb, Sn, and Tl contents decreased both with the distance to the Pb–Zn smelter as well as the soil depth, hinting that these elements were mainly originated from the Pb–Zn smelting operations and were introduced into soils through atmospheric deposition. Soil Ge was influenced by the smelter at a less extent, while the distributions of Co, Cr, and Ni were roughly even among most sampling sites and soil depths, suggesting that they were primarily derived from natural sources. The contamination status, as revealed by the geo-accumulation index (I _geo), indicated that In and Ag were the most enriched elements, followed by Sb, Bi, and Sn. In general, Cr, Tl, Co, Ni, and Ge were of an uncontaminated status.     

Mussel-based monitoring of trace metal and organic contaminants along the east coast of China using Perna viridis and Mytilus edulis

Green lipped mussels, Perna viridis, and blue mussels, Mytilus edulis, were collected from seven locations along the east coast of China in September and October 2001. The mussel tissues were analyzed for metals (Ag, As, Cd, Cr, Ni, Pb, Se, Zn, Cu, Fe and Hg), and trace organic contaminants including organochlorine compounds (OCs), polycyclic aromatic hydrocarbons (PAHs; based on 24 individual PAHs), polychlorinated biphenyls (PCBs) and petroleum hydrocarbons (PHCs). Maximum concentrations of Ag, As, Cd, Cr, Ni, Pb, Se, Zn, Cu, Fe and Hg in the mussel tissues were 0.14, 26.76, 5.31, 15.72, 4.78, 2.93, 7.40, 231.0, 54.17, 1002 and 317.3 microg/g dry weight respectively. Levels of DDTs, PAHs, PCBs and PHCs in the mussel samples were 14-640, 456-3495, 1-13 ng/g and 621-2863 microg/g dry weight, respectively. Results of this study indicated that contaminant levels were, in general, higher or at least comparable to those reported in other local or regional studies. Mussel samples collected in Chongming Dao in Shanghai and Jiao Zhou Wan in Qingdao had significantly higher levels of metal and trace organic contaminants among the seven sampling stations. Examination of the contaminant profiles suggests that PHCs originated from petrogenic sources, while both petrogenic and pyrolytic sources were important for PAHs. The generally high levels of metals and organochlorine compounds are probably the result of increasingly intense industrial activities along the east coast of China. An assessment of potential risks to human health due to consumption of the mussels was undertaken for the metals, PCBs, DDTs and chlordanes, and the results indicated that all metals, except Ni, could pose a health risk to heavy seafood consumers, while Hg appears to be of concern even for low level consumers.     

Analysis of heavy metal distribution in superficial estuarine sediments (estuary of Bilbao, Basque Country) by open-focused microwave-assisted extraction and ICP-OES

Open-focused microwave-assisted extraction and ICP-OES determination of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn from surface sediments of the estuary of Bilbao (Basque Country, North of Spain) was carried out. All the samples were collected at three different tributaries of the estuary (Asua, Galindo and Nerbioi-Ibaizabal) every two months during 1999. The digestion procedure was proposed from the conclusions of a fractionated factorial design, and the precision and accuracy of the method was verified using a certified reference sediment (RTC008-050). The results of the analysis were statistically treated by means of principal component analysis and correlation analysis. The principal component analysis of sediment data (32 samples × 9 metals) indicated different patterns of contamination regarding the tributary and sampling station. The two main patterns observed were a steady increment of the metal concentration along all the campaigns in the samples collected in the Galindo River and a seasonal variation in the Nerbioi-Ibaizabal River, with higher metallic content during summertime and lower content during wintertime.     

An assessment of metal contamination along the Irish coast using the seaweed Ascophyllum nodosum (Fucales, Phaeophyceae)

The relative abundance and variation of Cr, Co, Cd and Pb in Ascophyllum nodosum and intertidal surface sediments from six locations around the coast were assessed over six seasons. Higher Cd and Pb levels in Galway Docks and Cork Harbour were attributed to localised inputs of these metals from municipal and domestic waste, while at a reference site (Ballyconneely), high algal Cr concentrations were considered a function of geological setting rather than anthropogenic loading. Little seasonal variation was observed, with the exception of higher Co levels in plants in winter, associated with growth dynamics and increased fluvial inputs. In comparison with previously published data for metals in A. nodosum from the North Atlantic, with the exception of localised hot spots, the Irish coastline is still a relatively pristine environment. A. nodosum may be successfully and easily used as a biomonitor of metal contamination in coastal waters.