The ability of 2D hybrid structures formed by boron, nitrogen and carbon atoms (h-BNCs) as potential substrates for surface enhanced Raman spectroscopy (SERS) detection of dioxin-like pollutants is theoretically analyzed. The strong confinement and high tunability of the electromagnetic response of the carbon nanostructures embedded within the h-BNC sheets point out that these hybrid structures could be promising for applications in optical spectroscopies, such as SERS. In this work, two model dioxin-like pollutants, TCDD and TCDF, and a model h-BNC surface composed by a carbon nanodisk of ninety-six atoms surrounded by a string of borazine rings, BNC96, are employed for the simulation of the adsorption complexes and the static and pre-resonance Raman spectra of the adsorbed molecules. A large affinity of BNC96 by these pollutants is reflected on the large interaction energies obtained for the most stable stacking complexes, with dispersion being the most important contribution to their stability. The large vibrational coupling of some active modes of TCDF and, specially, of TCDD makes the Raman static spectra display a ‘pure’ chemical enhancement of one order of magnitude. On the other hand, due to the strong electromagnetic response of BNC96, confined within the carbon nanodisk, pre-resonance Raman spectra obtained for TCDD and TCDF display large enhancement factors of 108 and 107, respectively. Promisingly, laser excitation wavelengths frequently used in SERS experiments also provoke significant Raman enhancements, around 104, for the TCDD and TCDF signals. Both the strong confinement of the electromagnetic response within the carbon domains and the high modulation of the resonance wavelengths within the visible and/or UV ranges in h-BNCs should lead to a higher sensitivity than graphene and white graphene parent structures, solving one of the main disadvantages of using 2D substrates for SERS applications.

Rice cultivation is the main agricultural activity in Asia, and it results in an enormous amount of agricultural waste, that are usually disposed-off by burning, causing serious environmental health and climate problems. Pakistan is the tenth largest producer in the world and the fourth exporter of rice in the world. To date, there are no studies targeting Pakistan’s profile monitoring its contribution in open burning emissions from rice straw waste. This study presents the characterization of PCDD/Fs, PCBs and PAHs emissions from three samples of rice straw collected from the main rice cultivation regions of Pakistan (Punjab, Sindh and Azad Jammu and Kashmir) in relation to the role of metal-based agricultural additives. PCDD/Fs, PCBs and PAHs emissions were quantified using a fixed grid system biomass plant and measuring the macro-pollutants online and sampling the organic micro-pollutants and metals in isokinetic mode, followed by ISO and CEN standards methods. In addition, role of agrochemicals was monitored in terms of metal catalysis resulted in POPs emissions. This study provides the characterization of most relevant group of pollutants (metals, PCDD/Fs, PCBs and PAHs) as a result of agricultural waste combustion. The rice straw samples from AJK showed high values of organochlorine micro-pollutants compared to the values followed by samples from Punjab and Sindh, i.e., respectively, ∑PCDD/F (2594>1493>856 pg/Nm³) and ∑PCB (41>38>30 pg/Nm³). Whereas the organic micro-pollutants ∑PAH, indicators of incomplete combustion (PICs), were recorded high in the samples from Sindh followed by Punjab and AJK. This study supports the idea that the phenomena that lead to the formation of PCDD/F and PCB are influenced not only by poor combustion but also by the presence of metal catalysts or precursors in the burned fuel.