A new sediment P release risk index (SPRRI) for “in-situ” phosphorus (P) release risk in lake sediment, is developed based on diffusive gradients in thin films (DGT) technique, DGT induced flux in sediments (DIFS) model and sediment properties. SPRRI includes three sub-indexes, which contain (1) the labile P pool size, (2) resupply constant (r) and desorption rate (Dspt rate) for P transfer and (3) the molar ratio between iron (Fe) in sequential extraction for sediment P by bicarbonate-dithionite (BD) and aluminum (Al) by NaOH (at 25 °C), i.e. BD(Fe)/Al[NaOH25] in sediment solid. The first sub-index considers P release from (i) sediment with NH₄Cl-P+BD-P pool, i.e. the loosely sorbed P (NH₄Cl-P) plus iron associated P (BD-P), or (ii) sediment with NH₄Cl-P pool, respectively. The second and third sub-indexes reflect kinetic P desorption and resupply ability of solid phase, and the effect of P sequestration by Al hydroxide on P release, in turn. The inner relationship between SPRRI and sub-indexes, and their effects on P release risk are elucidated. SPRRI can be used to evaluate sediment P reactivity by five release risk ranks. For Lake Dianchi (China), P transfer dynamics, labile P pool, resupply ability and Al-P in sediment, and “external P-loading” control and affect P release risk in different regions, which is reflected by the spatial distribution map for SPRRI. The present SPRRI can be applied for lakes with (1) pH range varying from moderate acidity to weak alkalinity in waterbody and (2) NH₄Cl-P or NH₄Cl-P+BD-P pool in sediment solid.

The binding of metal ions with humic acid (HA) plays an important role in the aggregation of HA and the migration of metal ions in the environments. The effects of common cations (Na⁺, Mg²⁺, Ca²⁺ and Al³⁺) and heavy metal ions (Ag⁺, Cd²⁺, Cu²⁺, Cr³⁺ and Eu³⁺) on the aggregation of HA were investigated systematically by aggregation kinetics, spectroscopic techniques and molecular dynamic (MD) simulations. The critical coagulation concentration (CCC) of mono-, di- and trivalent cations could be predicted by the Schulze-Hardy rule. The aggregation of HA in the presence of Na⁺ and Ag⁺ was mainly due to the reduction of repulsive force and the hydrogen bonds between HA molecules. While the complexation of di- and trivalent cations with carboxylic/phenolic groups, or the cation-π interactions enhanced the intra- or inter-molecular bridges in HA and then contributed greatly to the aggregation of HA. Heavy metal ions could easily pass through the electric double-layer of HA compared with common cations. MD simulations further signified the strong aggregation ability of HA molecules in solutions containing high valence metal ions. These findings are important for understanding not only how the influence of metal ions on the aggregation of HA, but also the conditions which ions more efficient for aggregation.

Metals are released from biochar (BC) in either the free or dissolved organic carbon (DOC)-combined form. The complexation of metals with DOC influences their toxicity and bioavailability in the environment. The endogenous release of metal species with heterogeneous DOC from BC is very complex; this process has been neglected and remains unaddressed in the literature to date. In this study, the yield and chemical properties of labile DOC from BC were characterized, and the release of endogenous metal/metalloid elements (K, Mg, Mn, Fe, Al, Cu, and Si) and their species from BC with various pyrolysis temperatures and particle sizes were systematically investigated under various solution chemistries. The results showed that pyrolysis temperature of BC significantly influenced the yield and composition of DOC and DOC-metal/metalloid complexes, while particle size had lower impact. The yield of BC-derived DOC significantly decreased and the components gradually changed from low-molecular weight and low-aromaticity hydrophilic humic acid-like substances to complex high-molecular weight and high-aromaticity hydrophobic substances as pyrolysis temperature increased from 200 to 700 °C. The release of total dissolved metals decreased with increasing pyrolysis temperature, while the highest total dissolved Si was released from BC with the moderate pyrolysis temperature (500 °C). The metal elements were mainly released in the DOC-combined form, while the released Si was mainly in the free form in the neutral water environment. The release of DOC increased while that of dissolved metals decreased with increasing solution pH. The release of total dissolved metals/metalloids increased but the ratio of the DOC-combined metals/metalloids decreased with increasing solution ionic strength. These results provide new insight into the understanding of endogenous metal/metalloid release from BC in the natural environment.

Agricultural soil is one of the main sink for both heavy metals and nanomaterials (NMs). Whether NMs can impact heavy metals uptake or bioaccumulation in plants is unknown. Here, cucumber plants were cultivated in a multi-heavy metals contaminated soil amended with four types of NMs (SiO2, TiO2, ZnS and MoS2) separately for four weeks. Physiological and biochemical parameters were determined to investigate the impact of NMs on plant growth. Inductively coupled plasma mass spectrometry was employed to determine the metal content in plants. Results showed that none of the tested NMs impacted plants biomass, but all the NMs showed different degrees of reduction in heavy metals bioaccumulation in plant roots, stems and leaves. However, four NMs showed different degrees of reduction in macro and micro nutrients uptake. MoS2 decreased the bioaccumulation of heavy metals (As, Cd, Cr, Cu, Ni, Al, Ti and Pb) for 36.4–60.6% and nutrients (Mg, Fe, K, Si and Mn) for 40.1%–50.1% in roots. Exposure to MoS2 NMs also significantly increased 23.4% of Si in leaves, 205.6% and 83.9% of Mo in roots and stems, respectively. In general, the results of this study showed promising potential for NMs to reduce uptake of heavy metals in crop plants, especially MoS2 NMs. However, the negative impacts of perturbing nutrients uptake should be paid attention as well.

Concerning PM2.5 concentrations, rapid industrialization, along with increase in cardiovascular disease (CVD) were recorded in Pakistan, especially in urban areas. The degree to which air pollution contributes to the increase in the burden of CVD in Pakistan has not been assessed due to lack of data. This study aims to describe the characteristics of PM2.5 constituents and investigate the impact of individual PM2.5 constituent on cardiovascular morbidity in Karachi, a mega city in Pakistan. Daily levels of twenty-one constituents of PM2.5 were analyzed using samples collected at two sites from fall 2008 to summer 2009 in Karachi. Hospital admission and emergency room visits due to CVD were collected from two large hospitals. Negative Binominal Regression was used to estimate associations between pollutants and the risk of CVD. All PM2.5 constituents were assessed in single-pollutant models and selected constituents were assessed in multi-pollutant models adjusting for PM2.5 mass and gaseous pollutants. The most common CVD subtypes among our participants were ischemic heart disease, hypertension, heart failure, and cardiomyopathy. Extremely high levels of PM2.5 constituents from fossil-fuels combustion and industrial emissions were observed, with notable peaks in winter. The most consistent associations were found between exposure to nickel (5–14% increase per interquartile range) and cardiovascular hospital admissions. Suggestive evidence was also observed for associations between cardiovascular hospital admissions and Al, Fe, Ti, and nitrate. Our findings suggested that PM2.5 generated from fossil-fuels combustion and road dust resuspension were associated with the increased risk of CVD in Pakistan.

Release of fluoride from Quaternary sediments produces F-contaminated groundwater which threatens the health of millions of people worldwide. Despite the mechanisms of fluoride release from sediments are documented by numerous studies, it remains poorly understood that whether indigenous microbes participate in or not for the formation of F-rich groundwater by releasing fluoride from aquifer sediments. A microcosm-based approach, geochemistry and techniques of microbiology and molecular ecology were conducted together to investigate these mechanisms. Results show that microbes are abundant in high [F] groundwater containing at least 1129 operational taxonomic units (OTUs), and indigenous microbes can have an essential role in the mobilization of fluoride in sediments collected from aquifers in a typical fluorosis area in China. It also shows that for the sediments in this study, fluoride release (ca. 2 mg/L) is coupled with elevated concentrations of Ca (△ = 75 mg/L), Mg (△ = 33 mg/L), Al (△ = 0.2 mg/L) and Mn (△ = 1.4 mg/L). This suggests that the fluoride may source from the dissolution of F-bearing carbonate minerals and/or Al-Mn hydroxides in a local acidic environment. The findings provide additional insights into the biogeochemical circulation of fluoride in natural environment, especially in groundwater system and the development of effective strategies for the management of F-contaminated groundwater worldwide.

Sediment records are widely used to infer impact of atmospheric metal deposition in alpine lakes, however, the legacy effect and catchment erosion of historical pollutants could potentially affect metal influx into lakes. Here, we collect data (including six trace metals and three lithogenic elements) from well-dated sediment cores of seven alpine lakes in southeast Tibet, which is adjacent to southwest China. This area has a documented history of preindustrial pollution. Metals such as cadmium (Cd), zinc (Zn) and arsenic (As) are found at relatively low concentrations until a clear increase is observed after 1950s across lakes. This result is consistent with accelerating atmospheric metal deposition due to socio-economic development in the region. We observe no synchronous trend across lakes in the changes of lead (Pb), copper (Cu) and silver (Ag), which show no significant increase after ∼1950 over the last two centuries in most of the study lakes. The historical trends of ²⁰⁶Pb/²⁰⁷Pb ratio reflect an important source of anthropogenic Pb associated with preindustrial mining and smelting in this study region, suggesting a substantial impact of legacy contamination from ancient mines. Furthermore, the temporal variations in these six anthropogenic metals are largely accounted for by terrigenous elements (e.g. aluminum (Al) and titanium (Ti)) in most of the study lakes, and to a lesser degree by sediment grain sizes and organic matter content, suggesting a significant role of catchment erosion in modulating sediment metal signals. In all, this study highlights the legacy effect of historical pollutants may have enhanced the forcing of catchment erosion in modulating the sediment signals of anthropogenic deposition in southeast Tibet.

Chemical compositions of fog and rain water were measured between July 2017 and September 2018 at Sejila Mountain, southeast Tibet, where fog events frequently occurred in original fir forests at altitude 3950 m. Fog water samples were collected using a Caltech Active Strand Cloud Collector (CASCC), and rain samples were collected using a precipitation gauge. Differences were observed between fog water and rain composition for most analyzed ions. Ion abundance in fog water was Ca²⁺ > Cl⁻ > Na⁺ > SO₄²⁻ > Mg²⁺ > NH₄⁺ >K⁺ > NO₃⁻ whereas an order of Ca²⁺ > Na⁺ > Cl⁻ > Mg²⁺ > SO₄²⁻ > NO₃⁻ > K⁺ > NH₄⁺ was observed for rain water. All ion concentrations were higher in fog water than in rain water. Additionally, Ca²⁺ was the dominant cation in both fog and rain samples, accounting for more than half of all measured cations. NH₄⁺ and SO₄²⁻ concentrations were notable for being higher in fog than rain water when compared with other ions. For trace elements, Al, As, Mn and Se were the most abundant elements in fog water; only Al and As were detected in rain water. Seventy-two hour back-trajectory analysis showed that air masses during fog and/or rain events mainly came from the south of Sejila Mountain. Spearman correlation analysis and source contribution calculations indicated that both marine and terrestrial sources contributed to the observed ion concentrations. Considering the higher concentrations of NH₄⁺ and higher ratio of NH₄⁺/NO₃⁻ measured in fog than in rain, we suggest that quantification of fog nitrogen deposition and its ecological effect in this area should be given more attention.

Applications of aluminium (Al) salt or lanthanum (La) modified bentonite (LMB) have become popular methodologies for immobilizing phosphorus (P) in eutrophic lakes. The presence of humic substances, has been shown to inhibit this form of treatment due to the complexation with La/Al. However, the effects of other dissolved organic matter (DOM), especially that derived from phytoplankton (the dominant source in eutrophic lakes) are unknown. In this study, the interaction with La/Al of Suwannee River Standard Humic Acid Standard II (SRHA) and algae-derived DOM (ADOM) were investigated and compared. Differed to SRHA which was dominated by polyphenol-like component (76.8%, C1-SRHA), majority in ADOM were protein-like substance, including 41.9% tryptophan-like component (C2-ADOM) and 21.0% tyrosine-like component (C3-ADOM). Two reactions of complexation and coprecipitation were observed between SRHA/ADOM and La/Al. Complexation dominated at low metal inputs less than 10 μM and coprecipitation was the main reaction at higher metal inputs. For ADOM, the tryptophan-like component (C2-ADOM) was the important component to react with metal. The reaction rate for C2-ADOM with La were about two-third of that for C1-SRHA, indicating that the influence of C2-ADOM was significant during the P immobilization by La/Al-based treatment in eutrophic lakes. The P removal data in the presence of ADOM confirmed the significant inhibition of ADOM. In addition, based on the composition of coprecipitates and relatively biodegradable character of tryptophan-like substances (C2-ADOM), the coprecipitation of ADOM was assumed to reduce the stability of precipitated P in eutrophic lakes. The release of P from the potential biodegradation of the coprecipitates and thus the possible decline of the performance of P immobilization by La/Al-based treatments is an important work in the future.

Red mud, which is from the aluminum industry, is a potentially under-utilized resource. Technological processes for using low-cost red mud as an alternative precursor for detoxifying metal pollutants urgently need to be developed. In this study, we systematically investigated the feasibility of using red mud to detoxify metal-containing wastes (e.g., fly ash) via the formation of preferable crystalline phases. To understand the mechanism of metal detoxification by red mud, CuO, NiO, and ZnO were blended with red mud at different weight ratios and the mixtures were then subjected to ceramic-sintering. After sintering, the X-ray diffraction results revealed that all of the metals (i.e., Cu, Ni, and Zn) were able to be crystallographically incorporated into spinel lattices. Sintering the red mud at 1100 °C for 3 h effectively converted the metals into spinels. The mixing weight ratios strongly affected the efficiency of the metal incorporation. The red mud was able to incorporate 15 wt% of metal oxides. The incorporation mechanisms mainly occurred between the metal oxide(s) and hematite. Modified TCLP tests were conducted to further evaluate the metal stabilization performance of the red mud, which demonstrated the leachabilities of ZnO and the sintered red mud + ZnO product. The concentration of leached metal was substantially reduced after the incorporation process, thus demonstrating that red mud can be successfully used to detoxify metals. The results of this study reveal that waste red mud can be feasibly reused as a promising waste-to-resource strategy for stabilizing heavy metal wastes.