Raman spectroscopic quantification of graphene oxide in soil: Transport, surficial enrichment and environmental effects.

The transport and retention data in environmental media are indispensable for the hazard evaluations of graphene materials. Due to the complexity of soil, the transport of graphene is hard to quantify without isotope labeling. Herein, we developed 2D Raman mapping as a label-free technique to quantify graphene oxide (GO) in soil. After pre-treatment by hydrazine hydrate to quench its fluorescence, the quantification of GO in soil was achieved in the range of 0.1-1000 mg/L by measuring the average G-band intensity. In column transport experiment, the transport and retention of GO in soil depended on the solution chemistry. Lower pH and higher ionic strength hindered the transport of GO. In particular, Ca showed the most obvious retardation on the transport of GO. GO enriched in the surficial soil layer by several folds of the initial concentrations, and higher GO concentration led to more surficial enrichment. The sowing manner of seeds affected the soil enrichment of GO, too. The surficial enrichment of GO reduced its direct contact with seedling roots, resulting in the alleviation of GO toxicity. Our results provided a facile method to study the environmental behaviors of graphene and highlighted the crucial impacts of environmental media on the graphene toxicity.