Time-resolved characterization of organic compounds in PM2.5 collected at Oki Island, Japan, affected by transboundary pollution of biomass and non-biomass burning from Northeast China.

To evaluate the transboundary pollution of organic aerosols from Northeast Asia, a highly time-resolved measurement of organic compounds was performed in March 2019 at Oki Island located in Japan, which is a remote site and less affected by local anthropogenic sources. PM2.5, water-soluble organic carbon (WSOC) concentrations, and WSOC fraction in PM2.5 showed high values on March 22-23 (high-WSOC period (HWSOC)) when the air mass passed through the area where many fire spots were detected in Northeast China. Biomass burning tracers showed higher concentration, especially levoglucosan exceeded 1 µg/m3 during the HWSOC than the low-WSOC period (LWSOC). Notably, high time-resolved measurements of biomass burning tracers and back trajectory analysis during HWSOC revealed a difference in the variation of lignin pyrolyzed compounds and anhydrous sugars on 22 and 23 March. The air mass passed to different areas in Northeast China in which fire spots were detected, such as the eastern area on the 22nd and the western area on the 23rd. Almost-organic compounds also showed high concentration and strong correlations with levoglucosan and sulfate during HWSOC. Moreover, low-carbon dicarboxylic acids (e.g., adipic acid) and secondary products from anthropogenic volatile organic compounds (e.g., 2,3-dihydroxy-4-oxopentanoic, phthalic, 5-nitrosalicylic acids), also showed a strong correlation with sulfate ions during the HWSOC and LWSOC, respectively. These higher concentrations and strong correlations with levoglucosan and sulfate during the HWSOC propose that their generation could be enhanced by biomass burning. The ratios of organics (e.g., levoglucosan/mannnosan, pinic/3-methylbutane-1,2,3-tricarboxylic acids) suggest that the high concentrations of PM2.5 and WSOC observed during the HWSOC were caused by aged organic aerosols that originated from the combustion of herbaceous plants transported from Northeast China. Our findings indicate that biomass combustion in Northeast China could significantly affect the chemical compositions and the characterization of organic aerosols in downwind regions of Northeast China.

Impact of field biomass burning on local pollution and long-range transport of PM2.5 in Northeast Asia.

Biomass burning (BB), such as, crop field burning during the post-harvest season, emits large amounts of air pollutants (e.g., PM2.5) that severely impact human health. However, it is challenging to evaluate the impact of BB on PM2.5 due to uncertainties in the size and location of sources as well as their temporal and spatial variability. This study focused on the impacts of BB on local pollution as well as the long-range transport of PM2.5 in Northeast Asia resulting from a huge field BB event in Northeast China during the autumn of 2014. Air quality simulations using the Community Multiscale Air Quality (CMAQ) model were conducted in the year 2014 over the horizontal domains covering Northeast Asia, including the Japanese mainland. In the baseline simulation (Base), field BB emissions were derived from Fire INventory from NCAR (FINN) v1.5 for the year 2014. The model reasonably captured the daily mean PM2.5 mass concentrations, however, it underestimated concentrations in autumn around Northeast China where irregular field BB following the harvest occurred frequently. To address the underestimation of emissions from BB sources in China, another simulation with boosted BB sources from cropland area (FINN20_crop) was conducted in addition to the Base simulation. The model performance of FINN20_crop was significantly improved and showed smaller biases and higher indices of agreement between simulated and observed values in comparison to those of Base. To evaluate long-range transport of PM2.5 from BB sources in China towards Japan, CMAQ with brute-force method (CMAQ/BFM)-estimated BB contributions for Base and FINN20_crop cases were compared with Positive Matrix Factorization (PMF)-estimated BB contributions at Noto Peninsula in Japan. The CMAQ/BFM-estimated contributions from FINN20_crop were in greater agreement with the PMF-estimated contributions. The comparison of BB contributions estimated by the two contrasting models also indicated large underestimations in the current BB emission estimates.

[Validation study on a method for multiresidue analysis of pesticides in vegetables and fruits with supercritical fluid extraction].

Supercritical fluid extraction (SFE) was applied to extraction of pesticides from vegetables and fruits. Residues were extracted from homogenized samples mixed with water-absorbent polymer with supercritical carbon dioxide in a stainless steel tube, followed by elution with acetone. Co-extractives were removed by means of mini-column clean-up. Measurement was performed by GC-MS/MS. Calibration was achieved by preparing matrix-matched calibration standards to counteract matrix effects. With the Japanese method validation guideline as a reference, the method was assessed in 5 agricultural products spiked with 334 pesticides at 0.01 and 0.1 µg/g. Compounds at each level were extracted from 2 samples on 5 separate days. The trueness of the method for 189 pesticides in all samples was 70-120%, and the repeatability and within-run reproducibility were also consistent with the guideline. The trueness of the method for the other 71 pesticides was in the range of 50-70%, though the repeatability and within-run reproducibility were satisfactory. This method is available as a multiresidue analysis method for vegetables and fruits.

[Validation study of a method for multiresidue analysis of pesticides in cereals and pulses using supercritical fluid extraction].

Supercritical fluid extraction (SFE) was applied to extraction of pesticides from cereals and pulses. Residues were extracted from homogenized samples mixed with water-absorbent polymer and supercritical carbon dioxide in a stainless steel tube, followed by elution with acetonitrile. Co-extractives were removed by means of mini-column clean-up. Measurement was performed by GC-MS/MS. Calibration was achieved by preparing matrix-matched calibration standards to counteract matrix effects. With the Japanese method validation guideline for pesticide residues as a reference, the method was assessed in 5 agricultural products spiked with 334 pesticides at 0.01 and 0.1 µg/g. Compounds at each level were extracted from 2 samples on 5 separate days. The trueness of the method for 137 pesticides in all samples was 70-120%, and the repeatability and within-run reproducibility were also consistent with the guideline. The trueness of the method for the other 101 pesticides was in the range of 50-70%, though the repeatability and within-run reproducibility were satisfactory. This method is available as a multiresidue analysis method for cereals and pulses.

[Simultaneous determination of dichlorvos, trichlorfon and naled in fruits and vegetables by liquid chromatography with tandem mass spectrometry].

A method for simultaneous determination of Dichlorvos (DDVP), Trichlorfon (DEP) and Naled (BRP) in fruits and vegetables by liquid chromatography with tandem mass spectrometry (LC/MS/MS) was developed. Pesticides were extracted with ethyl acetate together with phosphoric acid and anhydrous sodium sulfate, followed by an ENVI-Carb cartridge cleanup. Phosphoric acid prevented BRP from being converted to DDVP during extraction of pesticides from the sample. When the sample was dissolved in acetonitrile in a silanized glass vial, BRP and DEP remained intact. Mass spectral acquisition was performed with a TurbolonSpray (ESI) interface in the positive mode by applying multiple reaction monitoring. In LC separation, an ODS column was used with acetic acid-ammonium acetate-methanol as a mobile phase. Recoveries from 8 fruits and vegetables at the fortification level of 0.1 microg/g were 75.0-91.8% for BRP, 70.2-88.9% for DDVP, and 77.3-92.1% for DEP. The detection limits of BRP, DDVP and DEP were 1, 2 and 2 ng/g, respectively.