May 25-26, 2012 Investigation of the Heavy Metals Contaminations in Water, Sediment and Tilapia in the Hou-Jing River International Conference on Environmental Quality Concern, Control and Conservation Graduate student of the Department of Marin Environmental Engineering, National Kaohsiung Marine University, Kaohsiung 81157, Taiwan Hau-Ying Lee*, Chun-Lan Huang, Chitsan Lin, Huei-Ya Huang

Outline 1. Introduction 2. Sampling and Analysis 3. Materials and Methods 4. Results and Discussion 5. Conclusions and Suggestions 2

Introduction The Houjin River is suffering pollution from the wastewaters of the five major industrial parks, including the Dashe Industrial Park, Renwu Industrial Park, Nantze Export Processing Zone, Formosa Plastics Renwu Plant, and Chinese Petroleum Corporation Kaohsiung Refinery, as well as the serious heavy metal pollution. 3

Due to the toxicity, persistence and bioaccumulation contained in heavy metals, heavy metal pollution is a highly significant issue for contaminants in soil, sediments, water, and biota; which not only causes significant damages to the ecosystems but also leads hazards to human health through the bioaccumulation effects in the food chain. 4

Source of Heavy Metal in Wastewater Pollution of Houjin River The possible main source of contamination in heavy metal pollution of Houjin River, which could come from the 305 metal surface processing industries in nearby rivers as well as some small factories without business registration and regulations. 5

Research Purpose Discuss the heavy metal content and distribution of water, sediments and Tilapia in upstream, middle and lower reaches of the Houjin River. Discuss the heavy metal correlation between the water, sediment and organisms in Houjin River. Discuss the level of heavy metal contamination of the overall environment in Houjin River. 6

Sampling Planning 7 Sampling Site Houjin River Basin ： Bakong Bridge, Dehui Bridge, Xingzhong Bridge Sampling Site Houjin River Basin ： Bakong Bridge, Dehui Bridge, Xingzhong Bridge Sampling Time 6 sampling from March to November, Sampling Time 6 sampling from March to November, Analytical Methods NIEA M104.01C (Inductively Coupled Plasma - Atomic Emission Spectrometry) NIEA M318.00C (Thermal Decomposition, Amalgamation, and Atomic Absorption Spectrophotometry) Analytical Methods NIEA M104.01C (Inductively Coupled Plasma - Atomic Emission Spectrometry) NIEA M318.00C (Thermal Decomposition, Amalgamation, and Atomic Absorption Spectrophotometry) Monitoring Items Arsenic, Cadmium, Chromium, Copper, Nickel, Lead, Zinc, Mercury Monitoring Items Arsenic, Cadmium, Chromium, Copper, Nickel, Lead, Zinc, Mercury

} 8 Bakong Bridge Dehuei Bridge Xingzhong Bridge ][

Sampling Method Water ： Refer to NIEA W104.51C of Environmental Analysis Laboratory, EPA, using stringed bucket to take surface river water. Sediment ： Refer to NIEA S104.30C of Environmental Analysis Laboratory, EPA, using stainless steel shovel to dig sediment in 0~15 cm, whereas three samples are taken from each test station and the sediments acquired are mixed into one single sample. Tilapia ： Capture using hand net. 9

Pre-Treatment – Water (Arsenic, Cadmium, Chromium, Copper, Nickel, Lead, Zinc) 10 Mix the water sample acidified for preservation and pour 100mL water sample into a 250mL beaker. Add 2 mL (1:1) of Nitric acid and 1 mL (1:1) of hydrochloric acid Place the beaker on top of the heating plate and control the temperature at 85 ℃ to heat. Heat until the volume becomes approximately 20 mL and cover the watch glass. Continue heating under reflux for 30 minutes. The water sample after digestion process diluted to 50 mL quantitatively with deionized water. Particles un-dissolved after putting aside applied with standing natural precipitation or centrifugation. Refer to NIEA W311.51

Pre-Treatment – Sediment (Arsenic, Cadmium, Chromium, Copper, Nickel, Lead, Zinc) 11 Remove the sample and place into the plastic beaker to undergo freeze-drying Take 0.5g of sample and place into the polypropylene plastic digestive tube of digestion vessels. Add 5 mL of H 2 O 2 and 5 mL of HNO 3, cover the watch glass and heat the sample in temperature of 95 ℃ under reflux for 10 minutes before cooling the sample. Add 2.5 mL of HNO 3, cover the watch glass and continue heating under reflux for 30 minutes. Evaporate the sample until 5 mL, cool the sample and add 1.0 mL of H 2 O and 1.5 mL of H 2 O 2. Heat the sample to 95 ℃ and allow the sample liquid to evaporate until 2.5 mL Finally dilute the sample and filter quantitatively to 50 mL Add 5mL of HCl, cover the watch glass and heat the sample in temperature of 95 ℃ under reflux for 15 minutes, then cool. Refer to the 3050B method formulated by the UPA of U.S.

Pre-Treatment- Tilapia (Arsenic, Cadmium, Chromium, Copper, Nickel, Lead, Zinc) 12 Cut open the organism and remove the Tilapia for freeze-drying Take 0.5g of sample and add to the digestive tube. Add 8 mL of concentrated nitric acid. Cover with the lid and place into the digestion vessels. Add deionized water to the digestive tube quantitatively to 50 mL Temperature1Heating time (min)Retaining time (min)

Analysis equipment Digestion vessels ： SYSTEMATIC DS-360 Inductively Coupled Plasma – Optical Emissions Spectrometer, ICP-OES: Perkin-Elmer Optima 2100DV, with a auto sampler (ASX-520) Mercury Analyzer: NIPPON INSTRUMENTS CORPORATION MA-2000, with a auto sampler (BC-1) 13

Exceeding Rates Compare the use of various heavy metal concentration with our regulations to identify the rate exceeding our regulation standards to confirm the contamination status of Houjin River. Apply water quality standards for surface water to the water as comparison standards. Compare the sediment with the standards of agricultural land for food crops. Compare the organisms with our health standards for aquatic animals. The calculation method is shown as follows ： Exceeding Rate= Number of Samples Exceeding our regulations Total number of samples ×100% 14

Heavy metals in water 15 Exceeding Rates:44.4% Exceeding Rates:66.7%

16 Exceeding Rates:27.8% Exceeding Rates:16.7%

Heavy metals in Sediment Exceeding Rates:5.56% 17

18 Exceeding Rates:22.2%

Enrichment Factor M i ： refers to the concentration value of certain metal in the sample. Fe i ： refers to the concentration value of iron in the sample. M c ： refers to the concentration value of certain metal in the crust. Fe c ： refers to the average concentration value for iron in the crust. Enrichment factor is an important parameter for evaluating the influence on the degree of heavy metal enrichment in soil and sediment from human. The degree of contamination in the sediment of river can be evaluated using the enrichment factor (EF) (Taylor, 1964). 19

20 Heavy metals in Tilapia Exceeding Rates:34.8%

21 Exceeding Rates:33.7%

Bioconcentration Factor (BCF) The magnification of the concentration of chemical substance in the water yielded using the bioconcentration factor in an organism. Under a steady status, the ratio between the concentration of chemical substance inside the organism and the concentration of the chemical substances in the water. C b ： Concentration of heavy metal in the organism. C w ： Concentration of heavy metal in water. 22

The Bioconcentration Factors of Various Heavy Metal in the Organism BCF ≧ 500 The chemical substance cannot be easily decomposed in the environment or may contaminate the environment or harm the health of human body due to bioaccumulation, bioconcentration and biotransformation. BCF<500 The chemical substance is regarded as low bioconcentration capability. 23 AsCdCrCuHgNiPbZn Max

Conclusions The water of Houjin River contains concentration of heavy metals, namely Cadmium, Copper, Mercury, and Zinc exceeding the surface water quality standards of our State; which exceeding rates are: Cadmium 44.4%, Copper 66.7%, Mercury 27.8%, and Zinc 16.7%, that merit paying attention to. The maximum value of Cadmium, Copper and Zinc detected from the sediment of Houjin River have far exceeded the regulatory standards by multiples (4.28 times, 2.5 times and 4.5 times), whereas the Cadmium and Copper have exceeding rate of 5.56% and Zinc 22.2% respectively. Arsenic is not detected in the sediment of Houjin River. 24

Suggestions To identify the correct position of contaminating source, the sampling site should be deployed intensively with long-term monitoring required to acquire the source of contamination precisely. To acquire the metal accumulation in the fish bodies, long- term monitoring is required on the heavy metal content in the various aquatic lives under the aquatic ecosystems, thereby to acquire the accumulating status and concentration of heavy metals in fish bodies. 25

26