Byung-Jun Park

Integrated biomarkers induced by chlorpyrifos in two different life stages of zebrafish (Danio rerio) for environmental risk assessment.

This study was performed to understand how chlorpyrifos (CHL) affects zebrafish (Danio rerio) embryos and adults, by exposing this model organism to various concentrations of the insecticide. The 96-h acute toxicity test to determine the effect of CHL on adult zebrafish yielded a LC50 of 709.43μg/L(-1). Small molecular weight proteins less than 25kDa and phospholipids were analyzed with MALDI-TOF MS/MS in order to compare expression patterns, revealing that some peaks were dramatically altered after CHL treatment. Whereas no acute toxicity was detected in the embryo toxicity test, malformation of zebrafish larvae was observed, with many individuals harboring curved spines. In an angiogenesis test on larvae of transgenic zebrafish, CHL did not have an inhibitory effect. Relative gene expression analyses using real-time polymerase chain reaction (RT-PCR) of DNA from zebrafish embryos revealed that different subtypes of cytochrome P450 (CYP450), such as CYP1A and CYP3A, were significantly up-regulated in response to CHL at a concentration of 400μg/L(-1) compared to the control. The expression level of NR1I2, a CYP gene transcriptional regulator, UGT1a1, and MDR1 were all up-regulated in the CHL-treated embryos. Finally, the expression level of acetylcholinesterase (AChE) and catalase (CAT) decreased, whereas that of superoxide dismutase (SOD) did not differ significantly. Our results suggest that the up-regulation of metabolic enzymes including CYP450 and MDR1 may be involved in CHL resistance in zebrafish.

Monitoring and risk assessment of polychlorinated biphenyls (PCBs) in agricultural soil collected in the vicinity of an industrialized area

Samples of agricultural soils possibly contaminated by polychlorinated biphenyls (PCBs) were collected from Anseong, Korea. The agricultural areas chosen have possibly been contaminated by nearby factories, either directly or via atmospheric deposition, and require monitoring. The concentrations of 29 out of 209 PCB congeners were determined at five sites using high-resolution gas chromatography/high-resolution mass spectrometry. Total concentrations of the 29 PCB congeners in soil samples obtained from each study site were 106.65, 149.15, 222.67, 166.15, and 118.28xa0pgxa0g−1 dry weight, respectively, with pentaCBs and hexaCBs giving the highest concentrations of the congeners studied. The total toxic equivalent (TEQ) for 12 PCBs from each site was 0.05, 0.11, 0.08, 0.05, and 0.04xa0ngxa0kg−1 dry weight, respectively. These values were mainly due to high TEQ values for PCB 126 (3,3′,4,4′,5-pentachlorobiphenyl) from each site (at 0.05, 0.10, 0.07, 0.04, and 0.03xa0ngxa0kg−1 dry weight, respectively). The TEQ values are much lower than the action level of 20xa0ng WHO–TEQxa0kg−1 recommended by the World Health Organization, but PCB concentrations in this area should be monitored nonetheless, since these manmade compounds bioaccumulate, thus threatening the ecosystem and human health.

Persistent Organic Pollutants (POPs) Residues in Greenhouse Soil and Strawberry–Organochlorine Pesticides

BACKGROUND: Residual organochlorine pesticides (OCPs) are chemical substances that persist in the environment, bioaccumulate through the food web, and pose a risk of causing adverse effect to human health and the environment. They were designated as persistent organic pollutants (POPs) by Stockholm Convention. Greenhouse strawberry is economic crop in agriculture, and its cultivation area and yield has been increased. Therefore, we tried to investigate the POPs residue in greenhouse soil and strawberry.METHODS AND RESULTS: Extraction and clean-up method for the quantitative analysis of OCPs was developed and validated by gas chromatography (GC) with electron capture detector (ECD). The clean-up method was established using the modified quick, easy, cheap, effective, rugged, and safe(QuEChERS) method for OCPs in soil and strawberry. Limit of quantitation (LOQ) and recovery rates of OCPs in greenhouse soil and strawberry were 0.9-6.0 and 0.6-0.9 μg/kg, 74.4-115.6 and 75.6-88.4%, respectively. The precision was reliable sincerelative standard deviation (RSD) percentage (0.5-3.7 and 2.9-5.2%) was below 20, which was the normal percent value. The residue of OCPs in greenhouse soil was analyzed by the developed method, and dieldrin, β-endosulfan and endosulfan sulfate were detected at 1.6-23, 2.2-28.4 and 1.8-118.6 μg/kg, respectively. Those in strawberry were not detected in all samples.CONCLUSION: Dieldrin, β-endosulfan and endosulfan sulfate in a part of investigated greenhouse soil were detected. But those were not detected in investigated greenhouse strawberry. These results showed that the residue in greenhouse soil were lower level than bioaccumulation occurring.

Acute toxicity and gene responses induced by endosulfan in zebrafish (Danio rerio) embryos

Abstract Endosulfan has been listed as a persistent organic pollutant, and is frequently found in agricultural environments during monitoring processes owing to its heavy use and persistent characteristics. This study was conducted to understand the effects of endosulfan on the development of zebrafish (Danio rerio) embryos by exposing them to a specific range of endosulfan concentrations. Exposing zebrafish embryos to endosulfan for 96 h yielded no acute toxicity until the concentration reached 1500 μg L−1, whereas malformed zebrafish larvae developed severely curved spines and shortened tails. About 50% of zebrafish larvae were malformed when exposed to 600 μg L−1 of endosulfan. Comparative gene expression using real-time quantitative polymerase chain reaction was assessed using endosulfan-exposed zebrafish embryos. CYP1A and CYP3A were significantly enhanced in response to endosulfan treatment. Two genes, acacb and fasn, encoding acetyl-CoA carboxylase b and fatty acid synthase proteins, respectively, were also up-regulated after treating zebrafish embryos with endosulfan. These genes are also involved in fatty acid biosynthesis. The genes encoding vitellogenin and Hsp70 increased in a concentration-dependent manner in embryos. Finally, biochemical studies showed that acetylcholinesterase activity was reduced, whereas glutathione S-transferase and carboxylesterase activities were enhanced in zebrafish embryos after endosulfan treatment. These biochemical and molecular biological differences might be used for tools to determine contamination of endosulfan in the aquatic environment.

Residual perfluorochemicals in the biochar from sewage sludge

Biochar has been recently considered as a candidate for soil amendment and soil remediation. Some pollutants have been screened in the biochar for safety purposes except for perfluorochemicals (PFCs). In this study, the contamination of biochars from plant residues and sewage sludge with perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) was examined. The total residual concentrations of PFOA and PFOS in the sludge biochar were 15.8-16.9 ng/g and these values did not decrease significantly after pyrolysis. On the other hand, these PFCs were not found in the biochar from plant sources. In conclusion, the use of the sludge biochar in the agricultural environment should be re-evaluated, since the concentrations of PFCs in the sewage sludge showed no significant decrease after thermal process.

Arsenic Contamination of Polished Rice Produced in Abandoned Mine Areas and Its Potential Human Risk Assessment using Probabilistic Techniques

BACKGROUND: This study was conducted to investi- gate the arsenic (As) contaminations in polished rice culti- vated nearby abandoned mine areas, and to estimate the potential health risk through dietary intake of As-enriched polished rice in each age-gender population. METHODS AND RESULTS: The As contents in poli- shed rice grown fifteen abandoned mine areas were analy- zed. The average daily intake (ADD) as well as probabili- stic health risk were estimated by assuming probability distribution of exposure parameters. The average total As concentration in polished rice was 0.09±0.06 mg/kg with a range of 0.02~0.35 mg/kg. For health risk assessment, the ADD values in all age-gender populations did not exceed the provisional tolerable daily intake (PTDI) of 2.1 µg/kg b.w./day for inorganic As. Cancer risk probability (R) values were 2.45~3.28×10 -4 and 2.51~5.75×10 -4 for all age population and gender population, respectively. Particularly, the R value, 5.75×10 -4 , for children less than six years old were estimated to be high. Hazard quotient (HQ) values were 0.23~0.31 and 0.11~0.33 for general population and age-gender population, respectively. CONCLUSION(s): The average R values assessed via intake of polished rice cultivated in abandoned mine areas exceeded the acceptable cancer risk of 10 -6 ~10 -4 for regula- tory purpose. Considering the HQ values smaller than 1.0, potential non-cancer toxic effects may not be caused by the long-time exposure through intake of As-contaminated polished rice.

Quantitative Analysis of Cinnamaldehyde, Cinnamylalcohol and Salicylaldehyde in Commercial Biopesticides Containing Cinnamon Extract Using Gas Chromatography - Flame Ionization Detector

BACKGROUND: In an environment-friendly agriculture, plant extracts have been perceived as alternatives of synthetic pesticides. The Environment-friendly Agriculture Promotion Act of Korea has approved cinnamon extract as a matter for the production of commercial biopesticides. Thirteen commercial biopesticides containing cinnamon extract have been marketed locally. However, the analytical method for the quality control of these biopesticides containing cinnamon extract has not been studied. METHODS AND RESULTS: Cartridge clean-up method for the determination of cinnamaldehyde, cinnamylalcohol and salicylaldehyde in biopesticides containing cinnamon extract was developed and validated by gas chromatography (GC). The clean-up method was optimized with HLB SPE cartridges for the bioactive substance in biopesticides containing cinnamon extract, and the eluate was analyzed by GC. The developed method was validated, and the LOQ and recovery rates of cinnamaldehyde, cinnamylalcohol and salicylaldehyde were 0.139, 0.067 and and 84.2, 86.5 and 82.1%, respectively. The contents of cinnamaldehyde, cinnamylalcohol and salicylaldehyde were analyzed using the developed method in the 13 commercial biopesticides. Results showed 0.06-17.37%,

Development of Analytical Method for Picoxystrobin in Agricultural Commodities Using GC/ECD and GC/MS

BACKGROUND: This study was conducted to develop analytical method for picoxystrobin in agricultural commodities using GC/ECD and GC/MS. METHODS AND RESULTS: Each steps of analytical method were optimized for determining picoxystrobin residues in various agricultural commodities. The developed methods include acetone extraction, n-hexane/saline water partition and florisil column chromatography for analysis of all samples (apple, potato, green pepper, hulled rice and soybean), and in addition to these steps, solid phase extraction (SPE) was used for analysis of green pepper and n-hexane/acetonitrile partition was used for analysis of hulled rice and soybean. The instrumental conditions were tested for quantitation in GC/ECD and for confirmation in GC/MS. Recovery was in the range of 86~109% with RSD 10.2% and the quantitation limits (LOQ) of method were 0.025 mg/kg in all agricultural commodities. CONCLUSION: The result showed that the developed method can be used to determine picoxystrobin residue in agricultural commodities.

Characteristics of Pesticide Runoff and Persistence on Agricultural Watersheds in Korea

To evaluate the exposure of non-point source pesticide pollution in agricultural watershed and to investigate pesticide distribution and runoff from agricultural land, paddy field, upland and orchard, this experiment was carry out during crop growing seasons. The pesticide were detected twenty pesticides (fungicide 4, insecticide 10, herbicide 6) in water of Neungchon agricultural watershed and detection concentrations were range 0.008~7.59 ppb. Most of the detection pesticides were using pesticides to rice paddy fields to control fungi, insects, weeds. During the crop cultivation, the pesticide were detected total thirty pesticides by pepper field soil 6, orchard soil 4, sesame field soil 3 and rice paddy field soil 5, and pesticide concentrations were range 0.001~0.109 ppm. Especially the herbicides were detected mainly in May and June in the stream water. The pesticide were detected thirty pesticides by fungicide 2, insecticide 6, herbicide 5 in water of Jungam Koseong agricultural watershed and detection concentrations were range 0.01~7.21 ppb. In regard to the detected pesticides, the concentration of individual pesticides measured in surface water of the study areas never exceeded guidelines for agriculture chemicals concerning water quality-effluent from paddy fields in Japan (Katayama, 2003). Runoff rate of pesticides was range 0.07~ 3.06 % from Kongju agricultural land to watershed after applied pesticides.

Perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) concentrations in the South Korean agricultural environment: A national survey

Abstract Research on the occurrence of perfluorochemicals (PFCs) such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in the agricultural environment is lacking, in spite of their potential risk via food chain transfer from aquatic and soil-plant systems to animals and/or humans. In the present study, for the first time, soil and water samples collected from 243 different agricultural sites adjacent to waste water treatment plants (WWTPs) belonging to 81 cities and 5 provinces with different levels of industrialization in South Korea were monitored for concentrations of PFOS and PFOA by use of solid phase extraction and liquid chromatography-tandem mass spectroscopy (LC-MS/MS). Significant mean concentrations of PFOA (0.001–0.007 µg L −1 water and −1 soil) and PFOS (0.001–0.22 µg L −1 water and −1 soil) were found in all samples. Concentrations of PFCs in soils were high, highlighting that soil is an important sink for PFCs in the agricultural environment. Samples from near WWTPs in Gyeongsang Province contained the highest concentrations of PFOS and PFOA, reflecting the concentration of heavy industry in the province. The concentrations of PFCs in agricultural water (most samples −1 ) and soils (most samples −1 ) from South Korea were less than acceptable guideline values, indicating that South Korea is not a hotspot of PFOS and PFOA contamination and that there is negligible risk to human and ecological health from these chemicals. However, further studies investigating the seasonal variation in PFOA, PFOS and other perfluorochemical concentrations in the agricultural environment are needed.