Compatibility of polar organic chemical integrative sampler (POCIS) with compound specific isotope analysis (CSIA) of substituted chlorobenzenes

Abstract

Compound specific isotope analysis (CSIA) is a powerful technique to demonstrate in situ degradation of traditional groundwater contaminants when concentrations are typically in the mg/L range. Currently, an efficient preconcentration method is lacking to expand CSIA to low aqueous concentration environmental samples. Specially for the H- and N-CSIA of heteroatom-bearing non-traditional compounds, the CSIA analytical detection limits are significantly higher than that of the C-CSIA. This work demonstrates the compatibility of polar organic chemical integrative sampler (POCIS) with C-, H-, and N-CSIA using four nitro- and amino-substituted chlorobenzenes that are common industrial feedstocks for numerous applications and are commonly detected in the environment at mg/L to μg/L range. Using lab experiments, we showed isotopic equilibrium in POCIS was achieved after 30 days with either a negligible (<0.5 ‰) or a constant shift for C (<1 ‰) and N (<2 ‰). Similar negligible (<5 ‰) or constant shift (<20 ‰) was evident for H isotope except for 3,4-dichloroaniline. The method quantification limits for the combined sorbent and membrane of one POCIS were comparable to that of the solid phase extraction (SPE) using 10 L water. Next, we demonstrated the field applicability of POCIS for C- and N-CSIA after a 60-day deployment in a pilot constructed wetland by showing <1 ‰ difference between the δ13C and δ15N obtained from POCIS and SPE. Finally, we evaluated whether the biofilm development on POCIS membrane could affect the isotope signature of the sampled compounds during field deployment. Although a diverse microbial community was identified on the membrane after a 60-day deployment, we did not observe significant isotope fractionation. This was likely due to either slower diffusion in the biofilm or microbial degradation of the sampled compounds. This work demonstrates the potential of using POCIS-CSIA as a simple, fast, and sensitive method for low-concentration contaminants, such as pesticides, pharmaceuticals, and flame-retardants.