Woo-Jin Shin

Tracing the geographical origin of beefs being circulated in Korean markets based on stable isotopes.

We have examined the carbon, nitrogen and oxygen isotopic compositions of American, Mexican, Australian, New Zealand and Korean beefs, which are currently being circulated in Korean markets, to check whether stable isotope ratios can identify their country of origin. Each beef exhibited statistically distinct isotopic compositions, especially in oxygen and carbon, because of the different isotopic compositions of their water and cattle feeds. Nevertheless, their isotopic compositions still showed some overlap, especially among USA, Australian, and Korean beefs, which sometimes resulted in significant misidentification when a single isotope was considered. However, the discrimination was generally successful when both the carbon and the oxygen isotopes were used.

Determining the geographical origin of Chinese cabbages using multielement composition and strontium isotope ratio analyses

Recently, the Korean market has seen many cases of Chinese cabbage (Brassica rapa ssp. pekinensis) that have been imported from China, yet are sold as a Korean product to illegally benefit from the price difference between the two products. This study aims to establish a method of distinguishing the geographical origin of Chinese cabbage. One hundred Chinese cabbage heads from Korea and 60 cabbage heads from China were subjected to multielement composition and strontium isotope ratio ((87)Sr/(86)Sr) analyses. The (87)Sr/(86)Sr ratio differed, based on the geological characteristics of their district of production. In addition, the content of many elements differed between cabbages from Korea and China. In particular, the difference in the content of Sr and Ti alone and the combination of Sr, Ca, and Mg allowed us to distinguish relatively well between Korea and China as the country of origin. The present study demonstrates that the chemical and Sr isotopic analyses exactly reflect the geology of the production areas of Chinese cabbage.

A multianalytical approach for determining the geographical origin of ginseng using strontium isotopes, multielements, and 1H NMR analysis.

Asian ginseng (Panax ginseng C.A. Meyer) is widely used as an Oriental medicine in the East Asian regions, particularly Korea and China. In the study, the strontium isotope ratios ((87)Sr/(86)Sr), multielements, and metabolite profiles of 35 ginseng samples collected from Korea and China were examined in an attempt to develop a method to distinguish the origin of ginsengs from the two countries. A multivariate statistical approach was performed to analyze the multielements and the (1)H nuclear magnetic resonance (NMR) data. Results of a t-test for Mg, Fe, Al, and Sc showed significant variation between Korean and Chinese ginsengs, indicating potential tracers for discriminating them. Discriminating between the ginsengs from the two countries was generally successful when both the (87)Sr/(86)Sr ratios and rare earth element (REE) contents were used together. Moreover, principal component analysis (PCA) derived from the (1)H NMR data revealed a significant separation between the ginsengs originating from the two countries. The major metabolites responsible for differentiation were sugars such as glucose, xylose, and sucrose. The results suggest that this multiplatform approach offers a comprehensive method to distinguish the origin of ginsengs.

Carbon isotope fractionation of benzene and toluene by progressive evaporation.

Evaporation is one of the key attenuation processes for near-surface volatile organic compounds (VOCs) in the upper soil zone. Evaporation experiments were performed to investigate the carbon isotope fractionation of benzene and toluene during progressive and non-equilibrium evaporation at room temperature. Considerable carbon isotope fractionation occurred during evaporative enrichment of benzene and toluene. The carbon isotope compositions of residual compounds increased exponentially with increasing evaporation. Thus, the remaining liquids become isotopically heavier, and the process follows a Rayleigh trend. This result is compatible with the direction of isotopic changes associated with both microbial degradation and volatilization of hydrocarbons previously observed in soil columns, but shows exactly the opposite behavior to previous equilibrium volatilization findings.

Comparison of the oxygen and hydrogen isotopes in the juices of fast-growing vegetables and slow-growing fruits.

We have analyzed the oxygen and hydrogen isotopic composition of juices from fruits and vegetables collected from a small orchard in order to investigate the differences in isotopic enrichment and evaporation intensity between fast-growing vegetables and slow-growing fruits grown under the same climatic conditions. The oxygen and hydrogen isotope levels were much higher in the juices of the fruits and vegetables than in the source waters in which they grew because of evaporation effects. According to our data, fast-growing vegetables are subject to greater evaporation than slow-growing fruits. An evaporation experiment using the source water showed that the oxygen and hydrogen isotopic composition of the 60-80% residual fraction was similar to that of the isotopically enriched grape juice, whereas those of the plume and tomato juices were very close to that of the 80-90% residual fraction, thus proving the effect of evaporation.

Seasonal and spatial variations in water chemistry and nitrate sources in six major Korean rivers

Seasonal and spatial variations in water chemistry and contaminant sources were investigated in six major rivers in South Korea that vary widely in drainage area and length. The dissolved-load content of the rivers varied seasonally, and some dissolved ions such as Cl− and NO3− showed large spatial differences in all of the rivers. The water type changed from Ca–HCO3 in the upper reaches to Na–Cl–NO3 in the lower reaches, indicating anthropogenic contamination in the lower reaches. Compared with two relatively pristine rivers (the Sumjin and Mankyung rivers), the other four rivers, which flow through agricultural and urban areas, registered much higher Cl− and NO3− concentrations. Statistical analysis showed that seasonal and spatial variations in water chemistry occurred in all the rivers. The nitrogen and oxygen isotopes of dissolved nitrate indicated that the rivers flowing through urban and agricultural areas were significantly affected by manure, sewage, or both.

Using stable isotope analysis to discriminate gasoline on the basis of its origin.

RATIONALE Leakage of gasoline and diesel from underground tanks has led to a severe environmental problem in many countries. Tracing the production origin of gasoline and diesel is required to enable the development of dispute resolution and appropriate remediation strategies for the oil-contaminated sites. METHODS We investigated the bulk and compound-specific isotopic compositions of gasoline produced by four oil companies in South Korea: S-Oil, SK, GS and Hyundai. The relative abundance of several compounds in gasoline was determined by the peak height of the major ion (m/z 44). RESULTS The δ(13)C(Bulk) and δD(Bulk) values of gasoline produced by S-Oil were significantly different from those of SK, GS and Hyundai. In particular, the compound-specific isotopic value (δ(13)C(CSIA)) of methyl tert-butyl ether (MTBE) in S-Oil gasoline was significantly lower than that of gasoline produced by other oil companies. The abundance of several compounds in gasoline, such as n-pentane, MTBE, n-hexane, toluene, ethylbenzene and o-xylene, differed widely among gasoline from different oil companies. CONCLUSIONS This study shows that gasoline can be forensically discriminated according to the oil company responsible for its manufacture using stable isotope analysis combined with multivariate statistical analysis.

Chemical and isotopic compositions of bottled waters sold in Korea: chemical enrichment and isotopic fractionation by desalination

A total of 54 Korean bottled waters were investigated to characterize their origins and types using elemental and isotopic composition, as well as to identify elemental and isotopic changes in desalinated marine water that arise due to desalination. The different types of bottled water displayed a wide pH range (3.42 to 7.21). The elemental compositions of still and sparkling waters were quite similar, whereas desalinated marine water was clearly distinguished by its high concentrations of Ca, Mg, B, and Cl. In addition, desalinated marine water had much higher isotope ratios of oxygen and hydrogen (-0.5 and -2‰, respectively) than still and sparkling waters (-8.4 and -57‰). The elemental composition of desalinated marine water was adjusted through post-treatment procedures; in particular, boron was greatly enriched during desalination processes. The carbon isotope compositions of dissolved inorganic carbon (δ(13)C(DIC) values) varied widely according to the origins of the bottled waters (-25.6 to -13.6‰ for still water, -31.2 to -26.7‰ for sparkling water, and -24.1 to -6.3‰ for desalinated marine water). This indicates that carbon isotopes in dissolved inorganic carbon are significantly fractionated by desalination processes and re-modified through post-treatment procedures. The results suggest that combined elemental and stable isotopic tracers are useful for identifying the origin of bottled water, verifying elemental and isotopic modifications during desalination processes, and characterizing various water types of bottled waters.

Stable Isotopic Fingerprinting for Identification of the Methyl Tert-Butyl Ether (MTBE) Manufacturer

Since the late 1990s, methyl tert-butyl ether (MTBE) contamination in groundwater aquifers has become a serious concern in many countries. This study focused on the carbon and hydrogen isotopic compositions of MTBE reagents produced by six manufacturers from three regions, to investigate the potential of utilizing stable isotopes in tracing the production origin of MTBE. The carbon and hydrogen isotopic compositions (δ13C and δD) of MTBE ranged from −31.0% to −26.4% and −101% to −54%, respectively, and exhibited different signatures according to the manufacturer. Two different supplies of MTBE produced by the same manufacturer, however, had different carbon isotopic compositions, with a deviation of approximately 0.6‰. δ13C values of MTBE were classified according to the area of production (Japan, Europe and the United States), allowing the data from this study to be aligned with those of previous reports. The results suggest that both δ13C and δD values cannot be used to apportion sources of MTBE in detail, but that it is possible to apply a fingerprinting technique, which classifies the country of production of MTBE, using δ13C values alone. Minimal carbon isotope fractionation was observed during the progressive evaporation of MTBE, following the Rayleigh fractionation trend. The impurities of MTBE reagents, in particular the water contents, cause the gas-phase diffusion coefficient to vary and subsequently impact isotope fractionation. These data indicate that although significant loss of MTBE occurs by evaporation, the isotopic composition of the remaining MTBE in contaminated sites can be used to identify its production origin.

Water quality impacts of irrigation return flow on stream and groundwater in an intensive agricultural watershed

Irrigation return flow can include contaminants derived from agricultural practices, and then deteriorate the quality of surface and subsurface water within the watershed. Thus, it is important to estimate the effect of irrigation return flow on water chemistry/quality. To do that water samples were collected between November 2004 and December 2005 from stream and groundwater in a small watershed that contains extensive rice paddy fields. The water isotopic compositions represented seasonal variation, particularly in downstream of main channel and the tributary. In April and May, water samples in the downstream and tributary could not be explained by three-component (soil water, groundwater and rainfall) hydrograph separation models (THSM). These results indicated that the stream water was affected by high evaporation and that another water body (e.g. quick return flow) impacted on THSM. Plot of Cl/NO3 and NO3/HCO3 showed that the water chemistry of all water samples was mainly regulated by soil water and groundwater. In addition, the water chemistry was related to water derived from rice paddy fields (WR) and manure. Manure impacted the water chemistry in tributary, one of the shallow groundwaters and the deep groundwaters, whereas that water in downstream was affected by WR. On a plot of δ15NNO3 and δ18ONO3 values, many samples were in a cluster indicative of manure and on a denitrification line. These imply that irrigation return flow characterized by denitrification processes was involved in determining the water chemistry. We suggest that chemical and multi-isotopes approach combined with the THSM is useful to elucidate the sources and processes controlling water chemistry in stream associated with rice paddy fields.