An online method using continuous flow isotope ratio mass spectrometry （CF-IRMS） interfaced with a Gasbench Ⅱ was presented to determine chlorine stable isotope composition. Silver chloride （AgCl） was quantitatively derived from chloride by using silver nitrate （AgNO3）, and then was reacted with iodomethane （CH3Ⅰ） to produce methyl chloride （CH3Cl）. A GasBench Ⅱ equipped with a PoraPlot Q column was used to separate CH3Cl from any other gas species. Finally, chlorine stable isotope analysis was carried out on CH3Cl introduced to the IRMS in a helium stream via an active open split. The minimum amount of Cl used in this method is of the order of 1.4 μmol. Inter-laboratory and inter-technique comparisons show that the total uncertainty incorporating both the precision and accuracy of this method is better than 0.007%. Furthermore, ten seawaters sampled from different locations have a narrow δ37Cl value range from -0.008% to 0.010%, with a mean value of （0.000±0.006）%. This supports the assumption that any seawater can be representative of standard mean ocean chloride （SMOC） and used as an international reference material.
Nitrate pollution in groundwater is a serious water quality problem that increases the risk of developing various cancers.Groundwater is the most important water resource and supports a population of 5 million in Anyang area of the southern part of the North China Plain. Determining the source of nitrate pollution is the challenge in hydrology area due to the complex processes of migration and transformation. A new method is presented to determine the source of nitrogen pollution by combining the composition characteristics of stable carbon isotope in dissolved organic carbon in groundwater. The source of groundwater nitrate is dominated by agricultural fertilizers, as well as manure and wastewater. Mineralization, nitrification and mixing processes occur in the groundwater recharge area, whereas the confined groundwater area is dominated by denitrification processes.
Chlorinated aliphatic hydrocarbons （CAHs）, significant contaminants in groundwater, can be characterized by stable isotopic compositions of carbon and chlorine. Previously published methods were of low analytical sensitivity or not ideal for natural samples with low concentrations of CAHs. This method is reported here to carry out simultaneously carbon and chlorine isotope analyses for mieromolar concentrations of dissolved CAHs. It was executed by extracting and converting CAHs to carbon dioxide and methyl chloride （CH3CI）. Specially, a continuous-flow interface GasBench Ⅱ was used to extract CH3CI for online chlorine isotope analysis. As a result, it greatly enhances the efficiency for isotope analysis by eliminating procedures for offline CH3CI preparation and separation. Sample size requirement was reduced to approximately 11 pmol chlorine. The standard deviation of δ^＋3C and δ^37CI for both TCE solvents and water samples was better than 0.30‰ and 0.20%0 （1σ）, respectively.Carbon and chlorine isotope analyses can be used as an important tool to study the sources of organic contaminants in groundwater and their behaviors in the aquifers. The method is applicable to manufacturers＇ products as well as a sample from a polluted site in principle, which will be validated in our field studies.
