Soil moisture has a strong impact on the fluorescence intensity of PAHs, which is undoubtedly posing a challenge for the development of rapid real-time fluorescence detection technology of PAHs in soil. In this work, NIR diffuse reflectance spectroscopy was used to correct the fluorescence spectra of PAHs in order to reduce the effect of the soil moisture. To establish the correction method, eight soil samples with different moisture contents and a given phenanthrene concentration (8 mg/g) were prepared. The fluorescence and NIR diffuse reflectance spectra were collected for of all samples. It was found that the fluorescence spectra of the soil samples that vary with the moisture content together with the NIR diffuse reflectance spectra were considered for the correction of the fluorescence intensity of phenanthrene related to the moisture content. The results showed that the ratio of the fluorescence intensity at 384 nm to the NIR diffuse reflectance spectrum absorbance at 5184 cm⁻¹ can be used as a correction factor to reduce the effect of the soil moisture on the fluorescence intensity of phenanthrene in the soil. The validity of the correction method was verified by the quantitative analysis of PAHs with different concentrations and soil moisture contents. The results showed better linearity between the fluorescence intensity and the concentration of PAHs after the correction (with a correlation coefficient R of 0.99) than before the correction (with R of 0.86). The relative prediction errors for three unknown samples decreased from 19%, 51% and 40% before the correction to 5%, 13% and 0.44% after the correction, respectively, indicating the feasibility of the detection of PAHs in the soil by the combination of fluorescence and NIR diffuse reflectance spectroscopy.

Cattle-derived biochar (CB), which is derived from industrial pyrolysis of cattle carcasses in harmless treatment plants, is a naturally occurring mineral form of carbonate-bearing hydroxyapatite (CHAP) with a small amount of elemental carbon. CB has 4.02% of carbonate content, which falls under the B-type substitution of CHAP. In this work, the Cd(II) sorption capacity of CB was determined to be 0.82 mmol/g, with 97.6% of the Cd(II) uptake contributing to CHAP and only 2.36% of the Cd(II) uptake contributing to the elemental carbon component. The calculation and linear combination fitting (LCF) of Cd L₃-edge X-ray absorption near-edge structure (XANES) analysis indicated that the contributions of Cd(II) species to CB presented the following order: ion exchange (57.6%–61.0%) > precipitation (24.4%–29.9%) > surface complexation (12.5%–13.4%). The depth dependent X-ray photoelectron spectroscopy (XPS) showed the presence of ion exchange, which is accompanied by intraparticle diffusion. LCF of XANES and Rietveld analysis of X-ray diffraction (XRD) demonstrated that Cd(II) was precipitated in the form of Cd₅H₂(PO₄)₄·4H₂O on the CB surface. Furthermore, the precipitate was directly observed and identified by scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS). Consequently, we revealed the intricate binding mechanism of Cd(II) to CHAP-rich CB and confirmed the importance of surface precipitation.

Southwestern China contains the largest and most well-developed karst region in the world, and the potentially toxic elements (PTEs) content in the soils of the region is remarkably high. To explore the internal and external control factors and sources of soil PTEs enrichment in this area and to provide a basis for the treatment of PTE pollution, 113 soil samples were collected from Hengxian County, a karst region in Guangxi Province, southwestern China. The importance of eighteen influencing factors including parent material, weathering, physicochemical properties, topography and human activities were quantitatively analyzed by (partial) redundancy analysis. The sources of PTEs were identified using the Pb isotope ratio and absolute principal component score/multiple linear regression (APCS-MLR) model. The contents of all soil PTEs were higher than the corresponding background values of Guangxi soils. The contents in Cu, Zn, Cd, Hg and Pb were the highest in the soil from carbonate rock. The factor group of geological background and weathering explained 26.5% for the accumulation and distribution of soil PTEs and the influence of physicochemical properties was less than 2% but increased to 25.6% through interaction with weathering. Fe (47.1%), Al (42.1%), Mn (22%), chemical index of alteration (12.8%) and clay (11.9%) were the key factors affecting the soil PTEs, while the influence of human activities was weak. Pb isotope ratio and APCS-MLR classified 62.8–74% of soil PTEs as derived from natural sources, whereas 18.23% and 18.95% were derived from industrial activities and agricultural practice/traffic emissions, respectively. The Pb isotope ratio showed that the natural sources account for up to 90% of the Pb in the soil from carbonate rock, the highest contribution among the studied soils. The results of the study can provide background information on the soil PTEs contamination in the karst areas of China and other areas worldwide.

The lag effect in the polar organic chemical integrative sampler (POCIS) equipped with a polyethersulfone (PES) membrane (POCIS-PES) is a potential limitation for its application in water environments. In this study, a POCIS with a poly(tetrafluoroethylene) (PTFE) membrane (POCIS-PTFE) was investigated for circumventing membrane sorption in order to provide more reliable concentration measurements of organic contaminants. Sampler characteristics such as sampling rates (RS) and sampler-water partition coefficients (KSW) were similar for POCIS-PES and POCIS-PTFE, indicating that partitioning into Oasis HLB as the receiving phase dominates the overall partitioning from the aqueous phase to the POCIS. Membrane sorption was quantified in both laboratory and field experiments. Although POCIS-PTFE showed minor membrane sorption, the PTFE membranes were not robust enough to prevent changes in the sorption of the pollutants to the inner Oasis HLB sorbent due to biofouling. This was reflected in significant ionization effects in the electrospray ionization (ESI) source during the LC-MS/MS analysis. Despite clear differences in the ionization effects, the two POCISs types provided similar time-weighted average (CTWA) concentrations after a two-week passive sampling campaign in surface water and the outflow of a wastewater treatment plant. This study contributes to a more detailed understanding of POCIS application by providing a quantitative evaluation of membrane sorption and its associated effects in the laboratory and field.

In recent years, numerous studies paid more attention to the molecular mechanisms associated with fluoride toxicity. However, the detailed mechanisms of fluoride immunotoxicity in bovine neutrophils remain unclear. Neutrophil extracellular traps (NETs) is a novel immune mechanism of neutrophils. We hypothesized that sodium fluoride (NaF) can trigger NETs activation and release, and investigate the related molecular mechanisms during the process. We exposed peripheral blood neutrophils to 1 mM NaF for 120 min in bovine neutrophils. The results showed that NaF exposure triggered NET-like structures decorated with histones and granule proteins. Quantitative measurement of NETs content correlated positively with the concentration of NaF. Mechanistically, NaF exposure increased reactive oxygen species (ROS) levels and phosphorylation levels of ERK, p38, whereas inhibiting the activities of superoxide dismutase (SOD) and catalase (CAT) compared with control neutrophils. NETs formation is induced by NaF and this effect was inhibited by the inhibitors diphenyleneiodonium chloride (DPI), U0126 and SB202190. Our findings described the potential importance of NaF-triggered NETs related molecules, which might help to extend the current understanding of NaF immunotoxicity.

Nitrate is one of the most common pollution sources in groundwater, particularly in highly vulnerable karst aquifers. The potential for nitrification and denitrification within karst aquifers varies in different settings depending on the extent of anthropogenic inputs, so that accurate identification of nitrate sources can be difficult. Geochemical data and dual nitrate isotopes were measured in this study, incorporating a Bayesian isotopic mixing model, and used to identify nitrate sources, nitrification and denitrification, and quantitatively determine nitrate sources under different extents of anthropogenic inputs in three karst catchments within Chongqing Municipality, SW China: Laolongdong (an urbanized area), Qingmuguan (a suburban village), and Shuifang Spring (a protected natural area). At the Laolongdong catchment, the groundwater was in a reducing condition and enriched in δ¹⁵NNO₃ (averaging 18.9 ± 6.9‰) and δ¹⁸ONO₃ (averaging 8.5 ± 4.6‰). Manure and sewage waste were the main contributing nitrate sources. A slope of 1.8: 1 of the dual isotopes suggested a denitrification process occurring in anaerobic conduit flow. Within the Qingmuguan catchment, groundwater had average δ¹⁵NNO₃ and δ¹⁸ONO₃ values of 9.7 ± 3.5‰, and 1.9 ± 3.4‰, respectively. The data showed evidence for nitrification, and the contribution of soil organic nitrogen was 52.1%, followed by a contribution of 44.8% from manure and wastewater. At the Shuifang Spring catchment, the mean δ¹⁵NNO₃ and δ¹⁸ONO₃ values in groundwater were 8.8 ± 2.9‰, 2.3 ± 4.6‰, respectively. Nitrification was the dominant process and most of the nitrate was derived from soil organic nitrogen. This study suggests that karst underground rivers overlain by urban land use undergo denitrification, while the suburban and relatively pristine karst aquifers are dominated by nitrification, allowing development of a conceptual model for nitrate sources and transformations in karst aquifers from the categories of land use (i.e., urban, suburban, and pristine areas).Anthropogenic activities can change biogeochemical nitrogen dynamics of vulnerable karst aquifers, such that the groundwater overlain by an urban settlement has undergone denitrification, while suburban and pristine areas have been dominated by nitrification.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants with a number of them being carcinogenic. One of the approaches to assess human exposure to PAHs is to measure their urinary metabolites, monohydroxyl polycyclic aromatic hydrocarbons (OH-PAHs), with a method allowing for high throughput and short turn-around time. We developed a method to quantify nine urinary OH-PAHs by using supported liquid phase extraction (SLE) and isotope dilution gas chromatography tandem mass spectrometry (GC-MS/MS). SLE demonstrated advantages over the traditionally used liquid-liquid extraction techniques. The target analytes with spiked deuterated and ¹³C-labeled internal standards were extracted from urine by SLE after enzymatic cleavage of the glucuronide and sulfate conjugates. The extracted analytes were then derivatized with N-Methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA), and analyzed by GC-MS/MS. Six solvent mixtures were evaluated as the SLE extraction solvent, and pentane:chloroform (7:3, v/v) was selected due to its best overall analytical performance. Method detection limits for the 9 analytes ranged from 2.3 to 13.8 pg/mL. Precision and accuracy were satisfactory. SLE and internal isotope labeled standard combination reduced matrix effect effectively. This new method using SLE sample preparation techniques coupled with GC-MS/MS proves applicable to urinary measurements for PAH exposure studies for general population.

Heavy metals in the topsoil affected adversely human health through inhalation, ingestion and dermal contact. The health risk assessment, which are quantified from soil heavy metals sources under different land use, can provide an important reference basis for preventing and controlling the soil heavy metals pollution from the source. In this study, simple statistical analysis and Positive Matrix Factorization (PMF) were used to quantify sources of soil heavy metals; then a health risk assessment (HRA) model combined with PMF was proposed to assess quantificationally the human health risk (including non-cancer risk and cancer risk) from sources under residential-land, forest-land and farm land. Xiang River New District (XRNQ) was chosen as the example and four significant sources were quantitatively analyzed in the study. For cancer risk, industrial discharge was the largest source and accounted for about 69.6%, 69.7%, 56.5% for adults under residential-land, forest-land and farm-land, respectively. For non-cancer risk, industrial discharge was still the largest significant source under residential-land and forest-land and accounted for about 41.7%, 39.2% for adult, respectively; while agricultural activities accounted for about 51.8% for adult under farm-land. The risk trend of children, including cancer risk and non-cancer risk, was similar with adults. However, the non-cancer risk areas of adults affected by industrial discharge was higher than that of children, while the cancer risk areas of adults were on the contrary. The new exploration was useful to assess health risk quantification from sources under different land use, thus providing certain reference in preventing and controlling the pollution from the source for local authorities effectively.

As one kind of phosphorus species, polyphosphate (poly-P) is ubiquitous in natural environments, and the potential interactions between poly-P and humic substances in the sediments or natural waters would influence the fate of poly-P in the environments. However, the mechanism of the interactions has not yet been understood clearly. In this work, the characteristics and mechanisms of the interactions between humic acids (HA) and two model poly-P compounds with various chain lengths have been investigated. Results show that a stable polyphosphate-HA complex would be formed through the noncovalent interactions, and hydrogen bond might be the main driving force for the binding process, which might be formed between the proton-accepting groups of poly-P (e.g., PO and P–O−) and the oxygen containing functional groups in HA. Our findings implied that the presence of humic substances in natural waters, soils and sediments would influence the potential transport and/or mobility of environmental poly-P.