Analysis of heavy metal and polycyclic aromatic hydrocarbon pollution characteristics of a typical metal rolling industrial site based on data mining.

With the transformation and upgrading of industries, the environmental problems caused by industrial residual contaminated sites are becoming increasingly prominent. Based on actual investigation cases, this study analyzed the soil pollution status of a remaining sites of the copper and zinc rolling industry, and found that the pollutants exceeding the screening values included Cu, Ni, Zn, Pb, total petroleum hydrocarbons and 6 polycyclic aromatic hydrocarbon monomers. Based on traditional analysis methods such as the correlation coefficient and spatial distribution, combined with machine learning methods such as SOM + K-means, it is inferred that the heavy metal Zn/Pb may be mainly related to the production history of zinc rolling. Cu/Ni may be mainly originated from the production history of copper rolling. PAHs are mainly due to the incomplete combustion of fossil fuels in the melting equipment. TPH pollution is speculated to be related to oil leakage during the industrial use period and later period of vehicle parking. The results showed that traditional analysis methods can quickly identify the correlation between site pollutants, while SOM + K-means machine learning methods can further effectively extract complex hidden relationships in data and achieve in-depth mining of site monitoring data.

Advances in Molecular and Microscale Characterization of Soil Organic Matter: Current Limitations and Future Prospects.

Soil organic matter (SOM) comprises a continuum of organic materials from granular organic debris to small organic molecules and contains more organic carbon than global vegetation and the atmosphere combined. It has remarkable effects on soil ecological functions and the global carbon cycle as well as the fate of pollutants in the terrestrial ecosystem. Therefore, characterization of SOM is an important topic in soil science, ecology, and environmental science. Chemical complexity and spatial heterogeneity are by far the two biggest challenges to our understanding of SOM. Recent developments in analytical techniques and methods provide the opportunity to reveal SOM composition at the molecular level and to observe its distribution in soils at micro- and nanoscales, which have greatly improved our understanding of SOM. This paper reviews the outstanding advances in SOM characterization regarding these two issues from target and nontarget analyses comprising molecular marker analysis, ultrahigh-resolution mass spectrometry analysis, and in situ microscopic imaging techniques such as synchrotron-based spectromicroscopy, nanoscale secondary ion mass spectrometry, and emerging electron and optical microscopic imaging techniques. However, current techniques and methods remain far from unlocking the unknown properties of SOM. We systematically point out the limitations of the current technologies and outline the future prospects for comprehensive characterization of SOM at the molecular level and micro- and nanoscales, paying particular attention to issues of environmental concern.

Pathway for the Production of Hydroxyl Radicals during the Microbially Mediated Redox Transformation of Iron (Oxyhydr)oxides.

The reduction of ferric iron (Fe(III)) to ferrous iron (Fe(II)) by dissimilatory iron-reducing bacteria is widespread in anaerobic environments. The oxidation of Fe(II) in aerobic environments has been found to produce hydroxyl radicals (•OH); however, the role of iron-reducing bacteria in the process has not been well understood. Here, Shewanella oneidensis MR-1-mediated redox transformation of four typical iron (oxyhydr)oxides and the production of reactive oxygen species were investigated. The results showed that the production of •OH was mainly determined by the insoluble Fe(II) formed during microbially mediated reduction and also mediated by the mineralogical phase. Moreover, this study for the first time observed the exogenetic iron-independent production of •OH by S. oneidensis MR-1, and the integrated pathway of •OH generation during the iron redox process was revealed. Superoxide (O2•-) was indicated as a key intermediate species that was produced by both abiotic and biotic pathways, and •OH was generated by both the exogenetic iron-dependent Fenton-like reaction and exogenetic iron-independent pathways. S. oneidensis MR-1 played a pivotal role in both the reduction of Fe(III) and the production of O2•-. These findings contribute substantially to our understanding of the generation mechanism of reactive oxygen species at oxidation-reduction boundaries in the environment.

Facet-Mediated Adsorption and Molecular Fractionation of Humic Substances on Hematite Surfaces.

Interactions between dissolved organic matter (DOM) and iron oxyhydroxides have important environmental and geochemical implications. The present study employed two hematite nanocrystals to investigate the adsorption and molecular fractionation of two typical humic substances (HSs) using electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). Hematite with a predominant exposure of {100} facets induced more pronounced adsorption and molecular fractionation of HSs than {001} facets, indicating that the interfacial adsorptive fractionation process of HSs was mediated by exposed facets of hematite. Further exploration of the surface OH groups of the two hematite nanocrystals confirms that the facet-mediated molecular fractionation of HSs was attributable to the abundance of singly iron-atom coordinated -OH sites on the hematite surfaces. Molecules with a high oxidation state and high aromaticity such as oxidized black carbon, polyphenol-like, and tannic-like compounds preferentially formed ligand-exchange complexes with singly coordinated -OH groups on the hematite surfaces, inducing the selective binding and molecular fractionation of HSs at the mineral-water interface. These results demonstrate that singly iron-atom coordinated -OH sites determine DOM adsorption and mediate molecular fractionation on hematite surfaces, and this contributes substantially to our understanding of the molecular mechanisms of iron oxyhydroxide-mediated molecular exchange of DOM in soils and/or sediments.

Iron plays an important role in molecular fractionation of dissolved organic matter at soil-water interface.

Adsorption of dissolved organic matter (DOM) onto soils plays an important role in the mobility and stabilization of organic carbon in soils; however, little attention has been paid to changes in the molecular components of soil DOM during adsorption on soils. In the present study, molecular fractionation of DOM induced by adsorption on a red soil was investigated using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The results indicated that compounds high in unsaturation or polarity or rich in oxygen had a high affinity to soil surfaces, while aliphatic compounds with few oxygenated groups and low polarity compounds were preferentially retained in solution. Among soil fractions with different particle sizes, the fine clay fraction with high iron content and surface area was the main contributor to the adsorptive fractionation of DOM. Comparison of the molecular fractionation of DOM derived from adsorption on soil with iron removed and on soil minerals with various iron contents and surface areas further indicated that iron containing minerals in the soil provided the major adsorptive sites and determined the molecular fractionation of DOM at the soil-water interface. The results provide molecular information for further understanding mechanisms underlying the persistence and mobility of organic carbon in soils.