Kongtae Ra

Assessment of heavy metal contamination and its ecological risk in the surface sediments along the coast of Korea

ABSTRACT Ra, K., Kim, E.-S., Kim, K.-T., Kim, J.-K., Lee, J.-M., and Choi, J.-Y., 2013. Assessment of heavy metal contamination and its ecological risk in the surface sediments along the coast of Korea. We studied the spatial distribution of heavy metal contamination and its ecological risk assessment in sediments from the Korean coast. Surface sediments collected from 12 coastal zones of Korea (total 200 sediment samples) along the west, south and east coast of Korea have been analyzed for heavy metals including Cr, Co, Ni, Cu, Zn, As, Cd, Pb and Hg using ICP-MS. Mean concentrations were 58.3 mg/kg for Cr, 10.2 mg/kg for Co, 24.3 mg/kg for Ni, 36.5 mg/kg for Cu, 122 mg/kg for Zn, 9.1 mg/kg for As, 0.25 mg/kg for Cd, 35.0 mg/kg for Pb and 0.046 mg/kg for Hg, respectively. Sediments sampled from heavily industrialized areas such as Shihwa, Masan, Gwangyang and Ulsan were highly contaminated with Cu, Zn, Cd and Hg. Significantly positive correlation among metals were observed (p<0.01). This suggests that sources of metal contamination were mainly attributed to anthropogenic inputs from surrounding environment, especially national industrial complexes that consist of iron, steel, machinery, electronics and petrochemical. The results of metal assessment indices indicated that the Korean coast sediments were moderately contaminated with Cu, Zn, As, Cd, Pb and Hg. The mean of metal enrichment levels decreased following the order of Cu>Hg>Cd>Zn>As>Pb>Co>Cr>Ni. Based on the comparison with sediment quality guidelines (SQGs), Cu, As and Zn levels at more than 40% of sediment samples exceeding TEL values are likely to result in potential adverse effects on sediment-dwelling organisms.

The extent and historical trend of metal pollution recorded in core sediments from the artificial Lake Shihwa, Korea.

The vertical distribution of trace metals in sediment cores was investigated to evaluate the extent and the historical record of metal pollution over 30 years in the artificial Lake Shihwa in Korea. A marked increase of trace metals after 1980 was observed due to the operation of two large industrial complexes and dike construction for a reclamation project. There was a decreasing trend of metal concentrations with the distance from the pollution source. The enrichment factor and pollution load index of the metals indicated that the metal pollution was mainly derived from Cu, Zn and Cd loads due to anthropogenic activities. The concentrations of Cr, Ni, Cu, Zn, As and Pb in the upper part of all core sediments exceeded the ERL criteria of NOAA. Our results indicate that inadequate planning and management of industrialization and a large reclamation project accomplished by dike construction have continued to strongly accelerate metal pollution in Lake Shihwa.

Susceptibility to oxidative stress and modulated expression of antioxidant genes in the copper-exposed polychaete Perinereis nuntia

To identify and evaluate potentially useful biomarkers for oxidative stress as early warning indices in the polychaete, Perinereis nuntia, we exposed P. nuntia to copper (Cu) and measured several biomarker enzymes (glutathione S-transferase; GST, glutathione peroxidase; GPx, Metallothionein-like protein; MTLPs, and catalase; CAT) and genes (Pn-GSTs, Pn-CAT, and Pn-MT) with a cellular oxidative index, reactive oxygen species (ROS) level. Accumulated Cu concentrations in P. nuntia increased in a time-dependent manner. Intracellular ROS reached high levels 6h after exposure in P. nuntia with an increase of GST activity and glutathione (GSH) content. Particularly, GSH in polychaetes showed a positive correlation with Cu contents accumulated in P. nuntia. Messenger RNA expressions of GST sigma and GST omega showed relatively high expressions at 50 μg/L of Cu exposure, even though the moderate increase of rest of GST isoforms was also observed. Also regarding long-term exposure, we reared P. nuntia in sediments for 15 days, and found that there was an obvious increase of Pn-GSTs, Pn-CAT, and Pn-MT genes with elevated concentrations of Cu and Cd in polychaete body, compared to initial levels, suggesting that P. nuntia in sediment was affected by metals as well as by other organic pollutants to induce oxidative stress genes and enzymes. These findings suggest that oxidative stress is a potential modulator of defense system of P. nuntia. Several potential biomarker genes are available as early warning signals for environmental biomonitoring.

Assessment of pollution and ecological risk of heavy metals in the surface sediments of Ulsan Bay, Korea

Heavy metal concentrations in the surface sediments of specially managed Ulsan Bay were investigated to determine metal distribution, pollution status and its ecological risk using pollution indices (enrichment factor and geo-accumulation index), potential ecological risk index and sediment quality guidelines (SQGs). The order of mean concentration (mg/kg) of metals was Zn (361.9) > Cu (95.6) > Pb (90.7) > Cr (64.7) > Ni (32.2) > Co (16.6) > As (15.8) > Cd (0.40) > Hg (0.16) in sediments of Ulsan Bay. Spatial distribution of metals in sediments showed a significantly higher concentration near industrial complexes, indicating that metal pollution is caused by anthropogenic sources. The results of enrichment factor (EF) and geo-accumulation index (Igeo) showed that sediments were significantly accumulated with Cu, Zn, As, Cd, Pb and Hg, indicating moderate to very severe enrichment (pollution) by these metals. Based on the potential ecological risk index, Hg and Cd posed a very high and a considerable potential ecological risk. Cu and As posed a moderate potential ecological risk, while, other metals (Cr, Co, Ni, Zn and Pb) rarely posed any potential ecological risk to the coastal environments. The sediments in Ulsan Bay showed a very high level of ecological risk, dominated by Hg and Cd. Metal concentrations in sediments were 80% for Cu, 96.7% for Zn, 50% for As, 70% for Pb and 50% for Hg above the threshold effects level (TEL), respectively.

Three novel superoxide dismutase genes identified in the marine polychaete Perinereis nuntia and their differential responses to single and combined metal exposures

To identify superoxide dismutase (SOD) genes and evaluate their usefulness as potential markers for monitoring metal toxicity in aquatic environment, we cloned, sequenced, and characterized 3 SOD genes (Cu/Zn-SOD1, Cu/Zn-SOD2, and Mn-SOD) from the marine polychaete Perinereis nuntia. The accumulated metal contents and expressions of 3 SOD genes were compared after exposure to single and combinations of heavy metals, As, Ni, and Pb. The deduced amino acid sequences of the 3 SODs had evolutionary conserved domains, such as metal binding sites, and signature sequences. The phylogenetic analysis revealed that Cu/Zn-SOD1, Cu/Zn-SOD2, and Mn-SOD were clustered with extracellular Cu/Zn-SOD, intracellular Cu/Zn-SOD and mitochondrial Mn-SOD, respectively, of other species. The accumulated contents of Ni and Pb increased significantly in a time - dependent manner after exposure to both single and combination of the metals. However, the concentration of As did not change significantly in the exposure test. The quantitative real-time polymerase chain reaction (PCR) array showed that the 3 SOD genes had differential expression patterns depending on the exposure condition. The expression of all SODs mRNAs was significantly elevated in response to Pb alone and in combination with As. The mRNA level of Cu/Zn-SOD1 was the highest after exposure to Pb alone, while that of Mn-SOD was remarkably enhanced after exposure to a combination of As and Pb. Exposure to Ni alone rapidly elevated the expression of Cu/Zn-SOD1 and Mn-SOD mRNA, which then gradually decreased. Exposure to As had no significant effect on the modulation of any of the SOD genes of P. nuntia. These results suggest that all SOD genes might play important roles in cellular protection as antioxidant enzymes against heavy metal toxicity via different modes of action in P. nuntia and might have the potential to act as indicators in an environment containing a mixture of metals.

Evaluation of Spatial and Temporal Variations of Water Quality in Lake Shihwa and Outer Sea by Using Water Quality Index in Korea: A Case Study of Influence of Tidal Power Plant Operation

The basin of Lake Shihwa is one of highly industrialized region of Korea and a current environmental issue of study area is the operation of tidal power plant (TPP) to improve water quality. The application of water quality index (WQI) which integrates five physiochemical parameters (transparency, DO, DIN, DIP and chlorophyll-a) of water quality in Lake Shihwa and outer sea during 2011~2012 were performed not only to evaluate the spatial and temporal distribution of the water quality but also to assess the effect of water quality improvement by the operation of tidal power plant. The higher WQI values were observed in monitored sites near the industrial complexes in Lake Shihwa and the outfall of wastewater treatment plants (WWTPs) in outer sea. This indicates that the quality of seawater is influenced by diffuse non-point sources from industrial, municipal and agricultural areas in Lake Shihwa and by point sources from the effluence of municipal and industrial wastewater throughout WWTPs in outer sea. Mean WQI value decreased from 53.0 in 2011 to 42.8 in 2012 of Lake Shihwa. Water quality has improved significantly after TPP operation because enhancement of seawater exchange between Lake Shihwa and outer sea leads to improve a hypoxic condition which is primarily a problem in Lake Shihwa. Mean WQI of outer sea showed similar values between 2011 and 2012. However, the results of hierarchical cluster analysis and the deterioration of water quality in summer season indicate that the operation of tidal power plant was not improved the water quality in the upper most area of Lake Shihwa. To successfully improve overall water quality of Lake Shihwa, it is urgently necessary to manage and reduce of non-point pollution sources of the basin of Lake Shihwa.

Magnetic characteristics of sediment grains concurrently contaminated with TBT and metals near a shipyard in Busan, Korea

Bottom sediments near shipyards are often susceptible to receiving accidental spills of TBT and metals or their degradation products from hull scraping of antifouling system paints applied prior to 2008, when the AFS Convention 2001 was not in force. We investigated TBT and metal contamination of sediments near the shipyards of a small marina located in Busan, Korea and found that they were highly contaminated with TBT, Cu, and Zn. To better understand the environmental impacts and to make an optimal remediation plan, we characterized individual antifouling fragments in terms of metal and TBT contents, magnetic properties, and grain-size. Coarse-sized individual antifouling fragments exhibited simultaneously high levels of TBT, metals and high magnetic susceptibility, and appeared to be a major source of pollution in the sediment. Therefore, magnetic separation in combination with size-separation appears to be a cost-effective remediation method to remove the TBT and metals from contaminated shipyard sediments.

Distribution and Pollution Assessment of Trace Metals in Core Sediments from the Artificial Lake Shihwa, Korea

Metal concentrations in creek water, sewer outlets and core sediments were analyzed to identify the potential origin of metal pollution and to evaluate the extent of metal pollution and potential toxicity of Lake Shihwa. Mean concentrations for dissolved metals in creek water and sewer outlets were 1.6~136 times higher than those in the surface seawater of Lake Shihwa. Metal concentrations in creek water from an industrial region were also higher than those from municipal and agricultural regions, indicating that the potential source of metal pollution in the study area might be mainly due to industrial activities. The vertical profiles of metals in core sediments showed an increasing trend toward the upper sediments. Extremely higher concentrations of metals were observed in the vicinity of Banweol industrial complex. The results of a geo-accumulation index indicated that Cu, Zn and Cd were highly polluted. By comparing the sediment quality guidelines such as TEL and PEL, six metals such as Cr, Ni, Cu, Zn, Cd and Pb levels in core sediments nearby industrial complex exceeded the PEL value. Mean PEL quotient (mPELQ) was used to integrate the estimate of potential toxicity for measured metals in the present study. Mean PELQs in core sediments from Lake Shihwa ranged from 0.2~2.3, indicating that benthic organisms nearby the industrial complex may have been adversely affected.

Molecular cloning and expression of novel metallothionein (MT) gene in the polychaete Perinereis nuntia exposed to metals

To report a novel metallothionein (MT) gene and evaluate its potency as a biomarker, we clone this MT gene and measured the expression levels in the metal-exposed polychaete Perinereis nuntia. Accumulated metal contents and metallothionein-like proteins (MTLPs), which have been recognized as potential biomarkers, were compared with the relative mRNA expressions of the MT gene of P. nuntia (Pn-MT). In addition, the metal-binding affinity was estimated by recombinant Pn-MT protein. Pn-MT having high cysteine residues with three metal response elements in the promoter region closely clusters with those of other invertebrates. The accumulation patterns of metals were dependent on the exposure times in lead (Pb), cadmium (Cd), and copper (Cu) exposure. Particularly, both MTLP levels and relative mRNA expressions of MT were increased with accumulated metal contents and exposure time in P. nuntia exposed to Pb and Cd. There was no significant modulation of the Pn-MT gene in polychaetes exposed to Zn and As. However, the metal-binding ability of the recombinant Pn-MT protein provides a clear evidence for a high affinity of MT to several metal elements. These results suggest that Pn-MT would play an important role in the detoxification and/or sequestration of specific metals (e.g., Pb and Cd) in P. nuntia and have potential as a molecular biomarker in the monitoring of the marine environment using a polychaete.

Study on the Characteristics and Non-point Source Pollution Loads in Stormwater Runoff of Shihwa Lake

We study the characteristic and total flux of non-point pollutants such as total suspended solids (TSS), chemical oxygen demand (COD), dissolved nutrients, total phosphorus (TP) and total nitrogen (TN) in the storm water runoff from urban streams and sewer outlets of Banweol Industrial Complex around Shihwa Lake. The concentrations of non-point pollutants were generally increased with increasing of the duration and intensity of rainfall. Mean TSS concentration of Ansan stream was higher than that of sewer outlets but mean concentrations of COD, TP and TN were approximately 2~5 times higher of sewer outlet than of urban stream. TSS showed statistically positive relationships with COD and TP but it had negative correlation with dissolved nutrients. There was a significant correlation between total flux of non-point pollutants in the storm water runoff and total basin area of each sewer outlet, showing that the highest runoff flux was observed at 3rd sewer outlet which represents the largest basin area from Banweol industrial complex. Total runoff fluxes for TSS, COD, TP and TN in this study were 187,536 kg, 17,118 kg, 922 kg, 13,519 kg, respectively. Given the basin area of sewer outlet in Banweol industrial complex which corresponds only 3% from total catchment area around Shihwa Lake, enormous amount of non-point pollutants will be entered into Shihwa Lake without any treatment. It is necessary to manage and reduce of various non-point sources and pollutants because the runoff of nonpoint pollutants during storm events should be deteriorating the water quality of Shihwa Lake. Our results provides useful informations on the development of best managements practices (BMPs) for effective implementation of total pollution loads management system of Shihwa Lake.