Unravelling structure evolution of dissolved organic matter during oxidation by persulfate: Insights from aromaticity and fluorescence analysis.

Persulfate advanced oxidation technology is widely utilized for remediating organic-contaminated groundwater. Post-remediation by persulfate oxidation, the aromaticity of dissolved organic matter (DOM) in groundwater is significantly reduced. Nevertheless, the evolution trends of aromaticity and related structural changes in DOM remained unclear. Here, we selected eight types of DOM to analyze the variation in aromaticity, molecular weight, and fluorescence characteristics during oxidation by persulfate using optical spectroscopy and parallel faction analysis combined with two-dimensional correlation spectroscopy analysis (2D PARAFAC COS). The results showed diverse trends in the changes of aromaticity and maximum fluorescence intensity (Fmax) among different types of DOM as the reaction time increases. Four types of DOM (humic acid 1S104H, fulvic acid, and natural organic matters) exhibited an initially noteworthy increase in aromaticity followed by a decrease, while others demonstrated a continuous decreasing trend (14.3%-69.4%). The overall decreasing magnitude of DOM aromaticity follows the order of natural organic matters ≈ commercial humic acid > fulvic acid > extracted humic acid. The Fmax of humic acid increased, exception of commercial humic acid. The Fmax of fulvic acid initially decreased and then increased, while that of natural organic matters exhibited a decreasing trend (86.4%). The fulvic acid-like substance is the main controlling factor for the aromaticity and molecular weight of DOM during persulfate oxidation process. The oxidation sequence of fluorophores in DOM is as follows: fulvic-like substance, microbial-derived humic-like substance, humic-like substance, and aquatic humic-like substance. The fulvic-like and microbial-derived humic-like substances at longer excitation wavelengths were more sensitive to the response of persulfate oxidation than that of shorter excitation wavelengths. This result reveals the structure evolution of DOM during persulfate oxidation process and provides further support for predicting its environmental behavior.

Can arsenic bioavailability be predicted in soils using in vitro gastro-intestinal simulation?

Many gastrointestinal simulation methods have been used to predict bioavailability, but the suitability of different methods for the same metal(loid)s varies widely, which inevitably affects the accuracy of human health risk assessment. Arsenic is a common and important contaminant in many contaminated land situations. It can be readily absorbed and has teratogenic and mutagenic toxicity. Therefore, in this study, four the most commonly used in vitro simulation methods (the Physiologically Based Extraction Test (PBET), In Vitro Gastrointestinal Method (IVG), Soluble Bioavailability Research Consortium (SBRC), the Unified BARGE Method (UBM)) were tested against an in vivo animal live model, to evaluate their effectiveness for the prediction of soil As bioavailability in 10 industrially contaminated soils. The soil As relative bioavailability (RBA) varied between 15% and 68% in the different soils. As bioaccessibility differed between the 4 gastro-intestinal simulation methods. Gastric phase of UBM (UBMG) predicted As relative bioavailability the best of the 4 assays (R2 = 0.81). This study provides theoretical and technical support to refine human health risk assessment of As in soils from urban industrial legacy contaminated sites.

Effects of freeze-thaw action on in vivo and in vitro bioavailability of arsenic in soils from derelict industrial sites.

Arsenic is a metalloid with carcinogenic properties and has been classified as a Category I carcinogen by the International Agency for Research on Cancer (IARC). Freeze-thaw processes affect the migration and transformation of soil heavy metals, as well as adsorption/desorption and redox reactions. However, there is limited research directly addressing the impact of freeze-thaw processes on the bioavailability of soil heavy metals. In this study, we focused on As and selected As-contaminated soil samples from three types of legacy sites in heavy industrial areas. Under controlled freeze-thaw experimental conditions, we utilized both in vivo and in vitro bioavailability measurement methods to investigate whether and how freeze-thaw processes affect the bioavailability of soil As. The results of this study showed that freeze-thaw processes reduced soil pH (P < 0.05), CEC, SOM, and particle size, with decreases of 0.33, 1.2 cmol/kg, 5.2 g/kg, and 54 µm, respectively. It also increased weight specific surface area (BET) (P < 0.05), with an increase of 300 m2/kg. Freeze-thaw processes increased the proportions of exchangeable (P < 0.05), carbonate-bound, and iron-manganese oxide-bound As (P < 0.05), but reduced the proportions of organic-bound and residual As (P < 0.05). Freeze-thaw processes significantly increased the relative bioavailability and bioaccessibility of As, with increases of 32 ± 9.6% and 13 ± 0.23%, respectively. Soil pH, SOM, BET and electronic conductivity (EC) were identified as factors which could contribute to the increased bioavailability of As due to freeze-thaw processes. These results provide new insights and evidence for refining the assessment of human health risks associated with heavy metal contamination in polluted soils.

[Implementation of a pretreatment device for an electronic nose].

A pretreament device was implemented for removing the interference of humidity on the baseline signal response of sensors in an electronic nose, which was used for rapid detection and real-time monitoring of volatile chlorinated hydrocarbons (VCHs) pollution in soil. The desiccant material was optimized, and the humidity removal performance and adsorpiton of VCHs was studied. The pretreatment device was evaluated by both the electronic nose and gas chromatography (GC) for its applicability in monitoring the PCE concentration in the desorption gas during the soil ventilation process. The following results were obtained: 1) A desiccant tube with anhydrous calcium chloride followed by a halogenated hydrocarbon separation tube was the best device, with a humidity removal rate of over 99%, and the baseline values of each sensor in the electronic nose were close to that of the control. 2) The desiccant device described above could continuously remove almost all the humidity from air with 75% humidity within 90 min, and the humidity removal rate remained above 95% within 120 min, while little interference was observed on the baseline of each sensor. 3) Little adsorption was observed by the pretreatment device, the relative error being only 3% - 5% between the concentration of VCHs before and after the filtration by the pretreatment device. 4) When applied for monitoring the remediation progress in a soil ventilation process, 99% of humidity was removed within 120 min from air with humidity of over 98%, and the data determined with the electronic nose and GC fitted each other very well, with R2 > 0.99. From the above, the pretreatment device connected with the electronic nose was considered to be applicable for monitoring the soil remediation process.

[Applicability of an electronic nose for detection of volatile chlorinated hydrocarbons in soil].

An electronic nose principally composed of a photo ionization detector (PID) was developed for rapid detection of volatile chlorinated hydrocarbons (VCHs) in contaminated soil. Removal of interference gas such as benzene homologues with a pre-filtration tube was analyzed with gas chromatography (GC). A standard gas generator was applied to generate different concentrations of perchloroethylene (PCE) and trichloroethylene (TCE) gas, with which the determine precision and reproducibility of the electronic nose were evaluated by comparison with GC. Finally, simulated contamination soil with three typical paddy soils in Yangtze river delta region were used for ventilation purification experiments, the change of VCHs concentrations in the ventilation gas was monitored, based on which the applicability of the electronic nose was evaluated for on-line detection of the on-going of the ventilation purification process. Results showed that a halogenated hydrocarbon RAE-SEP tube was effective to remove interference gas, with 80%-97% of benzene homologues such as benzene and ethyl benzene being removed while more than 90% of VCHs passed through. With PCE or TCE gas, a linear dependence was derived between the data determined with the electronic nose and GC, the linear slope being 1.012 and R2 > 0.99. The electronic nose showed data consistent with GC (R2 > 0.99, n = 47) when applied for monitoring the remediation progress in a soil ventilation process. The electronic nose is therefore possibly applicable for rapid determination of soil pollution by VCHs, improving the efficiency of pollution diagnosis and remediation.