Use of oyster, Crassostrea gigas, and ambient water to assess metal pollution status of the charting coastal area, Taiwan, after the 1986 green oyster incident

Most of the oyster mariculture beds in Taiwan are in areas located along the west of the island. One of these areas is the Charting coast, where green oysters were found in 1986. During this incident, which became internationally notorious, mass mortality occurred in the Charting oyster beds. After this discovery, measures were taken by the authorities to counter pollution which lead to the problem. The effectiveness of these pollution control actions was evaluated in this study. Two water column indicators, particulate and sediment, and oysters were sampled and analyzed for metals (Cu, Zn, Pb, Ni) in Charting and its neighboring areas, Kuen-Shen Lake and Shin-Da Harbor, and the control area/station, Dah-Pen Wan. The current study shows that copper and zinc concentrations in both oysters and particulates significantly decreased in the Charting area, compared with concentrations found during the period of the green oyster incident. Six years after the incident, the copper concentration in oysters had fallen from a high of 4400 μg/g dry weight to an average of 300±69 μg/g dry weight, figures similar to the copper concentration in 1982. The pollution control actions taken after the incident are believed to be the cause of this recovery of the coastal environment. Nevertheless, Charting still produced oysters with the highest copper and zinc concentrations among the areas investigated. Further measures currently being taken by the government, including removing the sediment of some portions of Erhjin Chi, should be able to bring the oyster copper concentrations down to the levels similar to those observed in the neighboring area, (average concentration below 200 μg/g dry weight or all time maximum concentration below 500 μg/g dry weight).     

Ecological risk assessment of arsenic and metals in sediments of coastal areas of northern Bohai and Yellow Seas, China

Distributions of arsenic and metals in surface sediments collected from the coastal and estuarine areas of the northern Bohai and Yellow Seas, China, were investigated. An ecological risk assessment of arsenic and metals in the sediments was evaluated by three approaches: the Sediment Quality Guidelines (SQGs) of the United States Environmental Protection Agency (USEPA), the degree of contamination, and two sets of SQGs indices. Sediments from the estuaries of the Wuli and Yalu Rivers contained some of the greatest concentrations of arsenic, cadmium, copper, mercury, lead, and zinc. Median concentrations of cadmium and mean concentrations of lead and zinc were greater than background concentrations determined for the areas. All sediments were considered to be heavily polluted by arsenic, but moderately polluted by chromium, lead, and cadmium. Current concentrations of arsenic and metals are unlikely to be acutely toxic, but chronic exposures would be expected to cause adverse effects on benthic invertebrates at 31.4% of the sites.     

Speciation of heavy metals in estuarine sediments in the northeast of Brazil

An analytical procedure involving a three-step sequential extraction was used to determine the chemical association of heavy metals (Zn, Cr, Mn and Fe) with the major phases (exchangable, reducible and oxidizable) in samples from a fishpond of estuarine sediments. The pond is located in the Capibaribe River estuary, within the boundaries of the city of Recife, in the State of Pernambuco in the northeast of Brazil. The total metal content was determined as well. All metals were extracted from the residual fraction at a percentage greater than 50%.     

Relationships between pesticides and organic carbon fractions in sediments of the Danshui River estuary and adjacent coastal areas of Taiwan

In order to understand the fate of pesticides in marine environments, concentrations of pesticides and different carbonaceous fractions were determined for surface sediments in the Danshui River and nearby coastal areas of Taiwan. The major compounds detected were tetrachlorobenzene, HCHs, chlordane, aldrin, DDDs, DDEs and DDTs. Total concentrations of pesticides in the sediments ranged from not detectable to 23 ng g(-1), with the maximum value detected near the discharge point of the marine outfall from the Pali sewage treatment plant. These results confirm that pesticides persist in estuarine and nearby coastal environments of the Danshui River well after their ban. Concentrations of total pesticides significantly correlate with concentrations of total organic carbon and black carbon in these sediments, suggesting that total organic carbon and black carbon regulate the distribution of trace organic pollutants in fluvial and coastal marine sediments.     

Green oysters caused by copper pollution on the Taiwan coast

The first case of green oysters (Crassostrea gigas) broke out along the Charting mariculture area of south-western Taiwan in January 1986. The green color was found to be due to high copper content in the oyster tissue. Since then, a long-term survey around this area shows that total dissolved copper ranges from 4.99 to 23.6 microg/liter and particulate copper ranges from 1.09 to 5.51 microg/liter in sea-water. The green oysters collected from the Erhjin Chi estuary on 26 January, 1989 gave the highest copper content, 4401+/-79 ppm dry wt. Other green oyster cases were occasionally observed in the Hsiangsan and Anpin mariculture areas. Meanwhile, an experiment of copper accumulation in oysters was conducted at three stations (south-western Taiwan) for up to 90 days. Multiple regression analysis indicates that the food pathway may predominate in copper accumulation by green oysters. This bioaccumulation experiment shows that the total uptake of copper per oyster is an exponential function of exposure time for the first 2 weeks with an accumulation rate of 214 ppm Cu/day and then levels off. The average values of concentration factors for oysters (about 5 x 10(5)) were very close to steady-state values under the natural conditions at each station.     

Matrix-bound phosphine in Antarctic biosphere

Phosphine (PH(3)) is a natural gaseous carrier of phosphorus in its geochemical cycles, and it might be of importance to the phosphorus balance of natural ecosystem. For the first time phosphine levels were investigated in the Earth's coldest, driest, and most southerly Antarctic biosphere. Matrix-bound phosphine (MBP) was found in sea animal guanos, ornithogenic sediments and soils. Phosphine concentrations varied with different sea animal guanos. Average phosphine concentrations in empire penguin, gentoo penguin, sea lion, skua and gull guanos were 2.54+/-1.28 ng kg(-1), 6.21+/-2.15 ng kg(-1), 9.12+/-4.66 ng kg(-1), 11.90+/-1.29 ng kg(-1) and 14.55+/-6.74 ng kg(-1), respectively. The contents of phosphorus in these various matrixes have an important effect on MBP concentrations. The levels of phosphine appeared an increasing tendency with the content of TP, IP and OP in sea animal guanos, ornithogenic sediments or soils. The correlation between PH(3) and Fe, Mn, Al in these matrixes was also analyzed and discussed. Phosphine showed an obviously positive correlation with Fe in sea animal guanos. However, excessively high Fe, Al and Mn may inhibit the formation of PH(3) in the ornithogenic soils or sediments in the Antarctic biosphere.     

Relationship between copper speciation in sediments and bioaccumulation by marine bivalves of Taiwan

This paper evaluates the relationships between copper species in sediments and accumulation by the purple clam (Hiatula diphos) and venus clam (Gomphina aeguilatera) collected from the field and culture (aquaculture) ponds in the polluted coastal area of Lukang, Taiwan. Sediment was sampled along with the molluscs, including oysters (Crassostrea gigas), purple clams (Hiatula diphos), rock-shells (Thais clavigera), venus clams (Gomphina aeguilatera), and hard clams (Meretrix lusoria), from two unique environments of Lukang during the period from August 1993 to July 1994. The data indicate that the total copper concentrations in sediments from culture ponds (185 microg g(-1)) was higher than those of the field (44.0 microg g(-1)). Copper species in sediments were analyzed by a sequential leaching technique. Results show that concentrations of various copper species in the sediments are in the range of 1.14 +/- 0.59 to 13.2 +/- 22.4 microg g(-1) and 0.36 +/- 0.24 to 133 +/- 36.7 microg g(-1) for the two environments, respectively. Also the exchangeable copper in sediment from culture ponds was 15 times higher than that from the field. In addition, the sum of exchangeable and copper carbonates had the highest percentages of copper in both the pond sediment (86.6 %) and the field sediment (50.7 %). Maximum copper concentrations (309 +/- 35.1 microg g(-1)) in oysters were much higher than those in the other benthic organisms by about 4-127 times. Similarly, the data also showed that copper concentrations in Thais clavigera were 12-32 times higher than those in other benthic organisms. Copper concentrations in various benthic organisms differed significantly (p < 0.05) from that in Thais clavigera. This capacity makes Thais clavigera a potential candidate for monitoring copper in marine sediments. In terms of copper species, the best correlation was generally obtained between copper carbonates in sediments and copper concentrations in Hiatula diphos (r = 0.886*). A strong multiple regression correlation (p < 0.05, r2 = 0.7894) also indicates that the copper carbonates may dominate as the available form of copper to Hiatula diphos from various environments in the Lukang coastal area under natural physicochemical conditions.     

Influence of parasitism on the use of small terrestrial rodents in environmental pollution monitoring

Bioaccumulation of cadmium, chromium, copper, manganese, nickel, lead and zinc in small terrestrial rodents – voles and their cestode parasite Paranoplocephala dentata was studied. Contents of Pb, Mn, Ni and Zn in the parasite were found to be higher than in the kidney and liver of the parasitized animals. Lead level in the cestode was 37 fold higher than in the liver of the infected rodents. Bioaccumulation factors of zinc, nickel and manganese in the cestode are mostly in the range from 2 to 4.5. Considering the different contents of manganese and zinc in livers of non-parasitized and parasitized rodents, kidney tissue was found to be more reliable than liver as an indicator of environmental pollution by manganese and zinc; the kidneys of parasitized animals showed no significant change in the concentrations of those elements that are accumulated in the cestode.     

Application of principal component analysis for the estimation of source of heavy metal contamination in surface sediments from the Rybnik Reservoir

The concentrations of metals, loss of ignition and nutrient (N, P) were determined in the bottom sediments of the Rybnik Reservoir (southern Poland). The mean concentrations of the metals in the bottom sediments were: Cd 25.8 microgram/g, Cu 451.7 microgram/g, Zn 1583.4 microgram/g, Ni 71.1 microgram/g, Pb 118.6 microgram/g, Cr 129.8 microgram/g, Fe 38782 microgram/g and Mn 2018.7 microgram/g. The bottom sediments are very heavily loaded with zinc, manganese, copper, nickel, phosphorus and lead (percentage enrichment factor), and cadmium, phosphorus and zinc (index of geoaccumulation). The increase of cadmium, lead, nickel and zinc concentrations was connected with the inflow of the contaminated water of the river Ruda and long-range transport. The contamination of the reservoir with copper and manganese resulted mainly from atmospheric precipitation. The variability of the bottom sediment loading with metals during the investigations was affected in the first place by changes in the concentration of iron, but also those elements whose concentrations in the bottom sediment were elevated compared to the concentrations in shale--cadmium, nickel and lead.     

Heavy metal distribution in marine sediments from the southwest coast of Spain

The latest version (1999) of the BCR-sequential extraction technique was used to determine the distribution of metals (Cu, Zn, Cd, Pb, Fe, Ni, Cr, and Mn) with major sedimentary phases (acid-soluble, reducible, oxidisable and residual) in samples from the southwest coast of Spain. The total metal content was also determined. The results showed that an extensive area along the coast (35 km long), near the joint mouth of the Tinto and Odiel Rivers, contains sediments with high concentrations of metals, with maximums of 649 mg/kg of Zn, 336 mg/kg of Cu, 197 mg/kg of Pb and 2.5 mg/kg of Cd. The values found for Cr, Ni and Mn are comparable to those in unpolluted areas. Based on the chemical distribution of metals, we found that Zn is the most mobile (i.e., it can pass easily into the water under changing environmental conditions). This metal showed the highest percentages in the acid-soluble fraction (the most labile), especially in the central coastal area, where the samples contained over 50% of this element associated with this fraction. This area close to the Tinto and Odiel river mouths also shows a significant increase in the mobility of Cd and Cu. In both cases the amount present in the residual fraction is lower, and the acid-soluble fraction is increased for Cd and the oxidisable fraction for Cu. However, the highest percentages of Fe, Cr and Ni are found in the residual fraction (84%, 89% and 75%, respectively), which implies that these metals are strongly bound to the sediments.     

Contamination status and potential release of trace metals in a mangrove forest sediment in Ho Chi Minh City,Vietnam

Can Gio district is located in the coastal area of Ho Chi Minh City, southern Vietnam. Discharge of wastewater from Ho Chi Minh City and neighboring provinces to the rivers of Can Gio has led to concerns about the accumulation of trace metals (As, Cu, Cr, Ni, Pb, and Zn) in the coastal sediments. The main objective of this study was to assess the distribution of As, Cu, Cr, Ni, Pb, and Zn in surface and core sediments and to evaluate the contamination status in relation to local background values, as well as the potential release of these selected trace metals from sediments to the water environment. Sediment characteristization, including determination of fine fraction, pH, organic matter, and major elements (Al, Fe, Ca, K, Mg, and S), was carried out to investigate which parameters affect the trace metal enrichment. Fine fraction and Al contents were found to be the controlling proxies affecting the distribution of trace metals while other sediment characteristics did not show any clear influence on trace metals’ distribution. Although As concentrations in the sediments were much higher compared to its reference value in other areas, the enrichment factor based on local background values suggests minor contamination of this element as well as for Cr, Cu, and Pb. Risk assessment suggested a medium to very high risk of Mn, Zn, and Ni under acidification. Of importance is also that trace metals in sediments were not easily mobilized by organic complexation based on their low extractabilities by ammonium-EDTA extraction.

     

Distribution and variability of redox zones controlling spatial variability of arsenic in the Mississippi River Valley alluvial aquifer, southeastern Arkansas

Twenty one of 118 irrigation water wells in the shallow (25-30 m thick) Mississippi River Valley alluvial aquifer in the Bayou Bartholomew watershed, southeastern Arkansas had arsenic (As) concentrations (<0.5 to 77 microg/L) exceeding 10 microg/L. Sediment and groundwater samples were collected and analyzed from the sites of the highest, median, and lowest concentrations of As in groundwater in the alluvial aquifers located at Jefferson County, Arkansas. A traditional five-step sequential extraction was performed to differentiate the exchangeable, carbonate, amorphous Fe and Mn oxide, organic, and hot HNO(3)-leachable fraction of As and other compounds in sediments. The Chao reagent (0.25 M hydroxylamine hydrochloride in 0.25 M HCl) removes amorphous Fe and Mn oxides and oxyhydroxides (present as coatings on grains and amorphous minerals) by reductive dissolution and is a measure of reducible Fe and Mn in sediments. The hot HNO(3) extraction removes mostly crystalline metal oxides and all other labile forms of As. Significant total As (20%) is complexed with amorphous Fe and Mn oxides in sediments. Arsenic abundance is not significant in carbonates or organic matter. Significant (40-70 microg/kg) exchangeable As is only present at shallow depth (0-1 m below ground surface). Arsenic is positively correlated to Fe extracted by Chao reagent (r=0.83) and hot HNO(3) (r=0.85). Arsenic extracted by Chao reagent decreases significantly with depth as compared to As extracted by hot HNO(3). Fe (II)/Fe (the ratio of Fe concentration in the extracts of Chao reagent and hot HNO(3)) is positively correlated (r=0.76) to As extracted from Chao reagent. Although Fe (II)/Fe increases with depth, the relative abundance of reducible Fe decreases noticeably with depth. The amount of reducible Fe, as well as As complexed to amorphous Fe and Mn oxides and oxyhydroxides decreases with depth. Possible explanations for the decrease in reducible Fe and its complexed As with depth include historic flushing of As and Fe from hydrous ferric oxides (HFO) by microbially-mediated reductive dissolution and aging of HFO to crystalline phases. Hydrogeochemical data suggests that the groundwater in the area falls in the mildly reducing (suboxic) to relatively highly reducing (anoxic) zone, and points to reductive dissolution of HFO as the dominant As release mechanism. Spatial variability of gypsum solubility and simultaneous SO(4)(2-) reduction with co-precipitation of As and sulfide is an important limiting process controlling the concentration of As in groundwater in the area.     

The Effect of Grain Size and Element Concentration in Identifying Contaminant Sources

The distribution of metal contaminants between different size fractions of marine sediments is well known. However, the use of size normalization techniques may alter the ability or usefulness in identifying potential sources in complex environments. In a reassessment of metal data from the shelf area of Sydney, Australia, the mud and sand fractions were investigated separately by PCA and PLS methodologies. The analyses were able to produce clear distinctions between industrial/urban sources when based on a suite of metals rather than individual (single-element) concentrations. Signature analysis by PLS with copper, lead, zinc, manganese, chromium, cobalt, nickel, and cadmium demonstrated the dispersion of the fine-grained contaminated material to the south in the East Australian Current. However, due to the commonality between many of the metals, a subset of four metals was used to define the signature. This significantly improved separation, showing clear plumes extending ～30 km from the source rivers.     

Geochemical partitioning of Co, Cr, Fe, Sc and Zn in polluted and non-polluted marine sediments

The partitioning of Co, Cr, Fe, Sc and Zn into three fractions (reducible by acidified hydroxylamine hydrochloride, oxidizable by acidified hydrogen peroxide, and the residual after the previous extractions) of Saronikos Gulf surface sediments was determined by using a sequential extraction technique. The metal concentrations were determined by Instrumental Neutron Activation Analysis. With the exception of Sc, the metal content in the reducible and oxidizable fractions increases in the polluted sediments near the Athens Sewage Outfall (ASO) and a Fertilizer Plant (FP). In the non-polluted sediments, the residual fraction is the most important carrier for all metals examined. Oxidizable Cr and Zn correlate well with the organic carbon content of the sediments, but the reducible fraction (mainly Fe/Mn hydroxides) is the most important sink for Co, Cr, Fe and Zn in the polluted sediments near the ASO. The pyrite-rich wastes from the FP are influencing the geochemical partitioning of the metals examined in the sediments in front of the FP and, partially, in the sediments near the ASO.     

Heavy metal speciation and mobility assessment of arid soils in the vicinity of Al Ain landfill, United Arab Emirates

Sixty-four surface soil samples taken in the vicinity of Al Ain landfill were analysed for cadmium, chromium, copper, nickel, lead and zinc by inductively coupled plasma spectroscopy. Extraction techniques were used to establish the association of the total concentrations of the six metals in the soil samples with their contents in the exchangeable, carbonate, iron/manganese oxides, and residual fractions. In the investigated soils, the recorded concentrations were as follows: 0.043 mg kg^-1 for cadmium, 19.1 mg kg^-1 for chromium, 53.3 mg kg^-1 for copper, 60 mg kg^-1 for nickel, 13.7 mg kg^-1 for lead, and 117 mg kg^-1 for zinc. Cadmium, chromium, nickel, lead and zinc concentrations in the investigated soil samples reflect the natural background values in shale, whereas copper is slightly enriched. I-geo (geoaccumulation index) values of the metals in the soils under study indicate that they are uncontaminated with cadmium, chromium, nickel, lead and zinc, but contaminated to moderately contaminated with copper. Heavy metal contents in the sediments were found to be significantly influenced by different physico-chemical parameters. The effect of these parameters can be arranged in the following order: clay fraction > carbonate fraction > silt fraction > organic matter fractions. A sequential extraction procedure showed that the total concentrations of the heavy metals are largely bound to the residual phase (retained 71.4% of cadmium, 77.8% of chromium, 75% of copper, 47% of nickel, 62.8% of lead, and 75.8% of zinc). A likely sequence of mobility in the investigated soils is as follows: chromium > lead > nickel > cadmium > zinc > copper.     

Relationship between carbonaceous materials and polychlorinated biphenyls (PCBs) in the sediments of the Danshui River and adjacent coastal areas, Taiwan

Persistent organic pollutants, POPs (e.g., polychlorinated biphenyls) can seriously and deleteriously affect environmental quality and human health. These organic pollutants are exhibiting high affinities to solid phases and thus, quickly end up in sediments. To better understand the role of carbonaceous materials in the transport and distributions of POPs in terrestrial and near-shore environments, concentrations of PCBs and carbonaceous materials (including total organic carbon, black carbon and total carbohydrates), were determined in surface sediments of the Danshui River and nearby coastal areas, Taiwan. Total concentrations of PCBs in the sediments ranged from non-detectable to 83.9 ngg(-1), dry weight, with the maximum value detected near the discharge point of the marine outfall from the Pali Sewage Treatment Plant. These results suggest that the sewage treatment plant has discharged PCBs in the past and the concentrations are still high due to their persistence; alternatively, PCBs are still being discharged in the estuarine and near-shore environment of the Danshui River. Organic carbon and black carbon concentrations correlated well with those of total PCBs in the sediments, suggesting that both organic carbon and black carbon significantly affect the distribution of trace organic pollutants through either post-depositional adsorption, or by co-transport of similar source materials. The field results demonstrate that black carbon and plays an important role in the general distribution of PCBs, while concentrations of some specific PCBs are affected by both black carbon and organic carbon concentrations.     

Concentration and fate of persistent organochlorine pesticides in estuarine sediments using headspace solid-phase microextraction

The concentration and fate of persistent organochlorine pesticides (OCPs) in estuarine surface sediments in Erh-jen and Lan-yang rivers, Taiwan were investigated using headspace solid-phase microextraction (HSSPME) method to evaluate the possible pollution potential and guideline for OCP concentrations in Taiwan. The HSSPME method exhibits a good analytical performance with low detection limits for OCP determination in sediment. In addition, results obtained using the developed HSSPME method were in good agreement with those obtained using Soxhlet extraction in a certified sample. The developed analytical method was further applied to the determination of concentrations of OCP residues in surface sediments from the estuaries of the selected rivers in Taiwan. A total of 20 surface sediments from each river was collected from 10 sampling stations. The total OCP concentrations in sediments from Erh-jen River ranged from 0.17 to 5.04 ng/g-dw with the mean values of 0.25–1.24 ng/g-dw for HCHs, 0.10–0.89 ng/g-dw for cyclodienes and 0.16–0.64 ng/g-dw for DDTs. The concentrations of OCPs in sediments from Lan-yang River were in the range 0.37–0.9 ng/g-dw with an average of lower than 0.5 ng/g-dw. HCHs and DDTs were abundant in the estuarine sediments from the selected rivers. Results obtained in this study show that the origin of OCPs in the surface sediments from Erh-jen River is a combination of erosion of the weathered soils and long-range atmospheric transport, while the OCP concentrations found in Lan-yang River could be regarded as the background levels of OCPs in Taiwan.     

Assessing the nature of the combined effects of copper and zinc on estuarine infaunal communities

Elevated levels of copper and zinc in sediment have been shown to adversely affect estuarine infauna. We investigated the additivity of the combined effects of copper and zinc on infaunal recolonisation through a manipulative field experiment in Orewa estuary, New Zealand, using defaunated sediment discs treated with these metals. The nature of their combined effects varied among infaunal taxa and the particular variables being examined. Additive effects were detected for species richness, for the mean log abundances of the polychaetes Prionospio sp. and Scoloplos cylindrifer and for the multivariate response of the community as a whole. Antagonistic effects were detected for the mean log abundances of total infauna and the polychaete Heteromastus sp. Characterising the potentially interactive nature of the combined effects of multiple heavy metals is essential in order to build predictive models of future environmental impacts of metal accumulation in estuarine sediments.     

Toxaphene residues from cotton fields in soils and in the coastal environment of Nicaragua

Toxaphene (camphechlor) was intensively used in the cotton growing fields of Nicaragua for decades with application rates as high as 31 kg ha(-1) in 1985. Although the use of this compound has recently been discontinued in the country, its intensive use in the past and its long persistence in soil allowed for the build up of large reservoirs of toxaphene in agriculture soils and a wide dispersal of residues in the environment. Measurements of toxaphene in coastal areas on the coast of the Pacific Ocean show that environmental concentrations are particularly high in the district of Chinandega, the traditional cotton growing region. Toxaphene residues measured in soils attained 44 microg g(-1) (dry weight) while concentrations in lagoon sediments attained 6.9 microg g(-1) (dry weight) near the mouth of the rivers flowing across the agricultural region. Measurements in aquatic biota showed concentrations as high as 1.6 microg g(-1) (dry weight) in the soft tissues of clams. The toxaphene reservoir in soils combined with the obvious persistence of this compound in soils and lagoon sediments allows predicting that toxaphene will remain in the coastal ecosystem at relatively high concentrations for many years. Toxic effects in lagoon fauna are likely to be observed especially in benthic species that may recycle this compound from sediments. Consumption of seafood, in particular of clams (Anadara spp.) from the more contaminated areas, may expose the population to unacceptably high intake of toxaphene, 30 microg d(-1) per person, with the diet.