Understanding the binding characteristics of copper (Cu) to different functional groups in soil dissolved organic matter (DOM) is important to explore Cu toxicity, bioavailability and ultimate fate in the environment. However, the methods used to explore such binding characteristics are still limited. Here, two-dimensional correlation spectroscopy (2DCOS) integrated with Fourier transform infrared (FTIR), 29Si nuclear magnetic resonance (NMR), 27Al NMR, and synchrotron-radiation-based FTIR spectromicroscopy were used to explore the binding characteristics of Cu to soil DOM as part of a long-term (23 years) fertilization experiment. Compared with no fertilization and inorganic fertilization (NPK), long-term pig manure fertilization (M) treatment significantly increased the concentration of total and bioavailable Cu in soils. Furthermore, hetero-spectral 2DCOS analyses demonstrated that the binding characteristics of Cu onto functional groups in soil DOM were modified by fertilization regimes. In the NPK treatment, Cu was bound to aliphatic C, whereas in the manure treatment SiO groups had higher affinity toward Cu than aliphatic C. Also, the sequence of binding of functional groups to Cu was modified by the fertilization treatments. Moreover, synchrotron-radiation-based FTIR spectromicroscopy showed that Cu, clay minerals and sesquioxides, and C functional groups were heterogeneously distributed at the micro-scale. Specifically, clay-OH as well as mineral elements had a distribution pattern similar to Cu, but certain (but not all) C forms showed a distribution pattern inconsistent with that of Cu. The combination of synchrotron radiation spectromicroscopy and 2DCOS is a useful tool in exploring the interactions among heavy metals, minerals and organic components in soils.

The synthesis of clay-biochar composite has been recognized as an effective way to enhance the removal of pollutants. The interaction between clay mineral and biomass during thermal pyrolysis and the sorption capacity for ionic/nonionic organic containments have not been elaborated. In this study, two types of biochar were obtained from pyrolytic carbonization of the cellulosic-rich corn straw (C) and lignin-rich pine wood (P) at 500 or 700 °C. Typical clay minerals kaolinite and montmorillonite were selected to prepare clay-biochar composite. The results showed that the addition of clay mineral could strengthen dehydration reaction of corn straw biomass and reinforce its carbon structure. Montmorillonite-biochar composite owned more CC functional groups and porous structure than kaolinite-biochar composite. The addition of clay minerals could promote electrostatic attraction of ionic formed norfloxacin (NOR) on clay-pine wood biochar. However, the sorption capacity of nonionic diethyl phthalate (DEP) adsorption on clay-corn straw biochar decreased, owing to that clay increased the compactness of the biochar carbon structure, thus inhabited hydrophobic partition of nonionic organic compounds on disordered carbon fraction. The results from this study provide insights into the suitable contaminated site remediation by clay-biochar composite.

Elucidating the mechanisms of heavy metal (HM) adsorption on clay minerals is key to solving HM pollution in soil. In this study, the adsorption of four HM atoms (As, Cd, Cr, and Hg) on the illite(001) surface was investigated using density functional theory calculations. Different adsorption configurations were investigated and the electronic properties (i.e., adsorption energy (Eₐd) and electron transfer) were analyzed. The Eₐd values of the four HM atoms on the illite(001) surface were found to be As > Cr > Cd > Hg. The Eₐd values for the most stable adsorption configurations of As, Cr, Cd, and Hg were −1.8554, −0.7982, −0.3358, and −0.2678 eV, respectively. The As atoms show effective chemisorption at all six adsorption sites, while Cd, Cr, and Hg atoms mainly exhibited physisorption. The hollow and top (O) sites were more favorable than the top (K) sites for the adsorption of HM atoms. The Gibbs free energy results show that the illite(001) surface was energetically favorable for the adsorption of As and Cr atoms under the influence of 298 K and 1 atm. After adsorption, there was a redistribution of positions and reconfiguration of the chemical bonding of the surface atoms, with a non-negligible influence around the upper surface atoms. Bader charge analysis shows electrons were transferred from the surface to the HM atoms, and a strong correlation between the valence electron variations and the adsorption energy was observed. HM atoms had a high electronic state overlap with the surface O atoms near the Fermi energy level, indicating that the surface O atoms, though not the topmost atoms around the surface, significantly influence HM adsorption. The above results show illite(001) preferentially adsorbed As among all four investigated HM atoms, indicating that soils containing a high proportion of illite might be more prone to As pollution.

Heavy metal pollution is very common in soils. Soils are complex systems including minerals, bacteria, and various other substances. In Cd(II) contaminated soil, the combined effects of clay minerals and heavy metals on bacterial biofilm and Cd(II) adsorption are unappreciated. Our study showed that the combination of clay minerals (goethite, kaolinite, and montmorillonite) and heavy metals promoted Serratia marcescens S14 biofilm development significantly more than clay minerals or Cd(II) alone. The amount of biofilm after binary treatment with clay minerals and Cd(II) was 2.3–7.3 times than that in control. Mineral-induced cell death and the expression of the fimA, bsmA, and eps were key players in biofilm formation. Binary treatment with montmorillonite and Cd(II) significantly enhanced biofilm development and consequently increased the adsorption of Cd(II). Cd(II) removal is the result of co-adsorption of bacteria and minerals. Bacterial biofilm played an important role in Cd(II) adsorption. FTIR spectroscopy showed the components of biofilm were not affected by minerals and revealed the functional groups –OH, –NH, –CH₂, –SH, –COO participated in Cd(II) immobilization. Our findings are of fundamental significance for understanding how minerals and Cd(II) affect biofilms and thereby enhance Cd(II) adsorption and predicting the mobility and fate of heavy metals in heavy metal-contaminated soil.

The sorption and desorption behaviour of samarium (Sm), an emerging contaminant, was examined in soil samples at varying Sm concentrations. The obtained sorption and desorption parameters revealed that soil possessed a high Sm retention capacity (sorption was higher than 99% and desorption lower than 2%) at low Sm concentrations, whereas at high Sm concentrations, the sorption-desorption behaviour varied among the soil samples tested. The fractionation of the Sm sorbed in soils, obtained by sequential extractions, allowed to suggest the soil properties (pH and organic matter solubility) and phases (organic matter, carbonates and clay minerals) governing the Sm-soil interaction. The sorption models constructed in the present work along with the sorption behaviour of Sm explained in terms of soil main characteristics will allow properly assessing the Sm-soil interaction depending on the contamination scenario under study. Moreover, the sorption and desorption Kd values of radiosamarium in soils were strongly correlated with those of stable Sm at low concentrations (r = 0.98); indicating that the mobility of Sm radioisotopes and, thus, the risk of radioactive Sm contamination can be predicted using data from low concentrations of stable Sm.

The contamination of ground water with arsenic is a great public health concern. This paper discusses the possible formation mechanism of high As groundwater; identify the main influences of natural and anthropogenic factors on As occurrence in groundwater; and finally estimates As-induced potential health hazards in an intensive agricultural region, Datong Basin (Northern China). Our findings indicate that the predominant controlling factors of As in groundwater can be divided into natural factors and anthropogenic activities. Natural factors can be classified as natural potential source of As, environmental geological characteristics and hydrochemical conditions; anthropogenic activities are manifested in industrial coal mining, domestic coal burning, agricultural irrigation return flow and excessive application of fertilizers, and groundwater exploitation. Microbial and/or chemical reduction desorption of arsenate from Fe-oxide/hydroxide and/or clay minerals, As-bearing Fe-oxide/hydroxide reduction coupled with sulfate reduction, and competition with phosphorus are postulated to be the major process dominating As enrichment in the alkaline and anoxic groundwater. In addition, age-dependent human health risk assessment (HHRS) was performed, and high risk values reveal a high toxic and carcinogenic risk of As contaminate for population who is subject to the continuous and chronic exposure to elevated As.

Microbes indigenous to oil sands tailings ponds methanogenically biodegrade certain hydrocarbons, including n-alkanes and monoaromatics, whereas other hydrocarbons such as iso- and cycloalkanes are more recalcitrant. We tested the susceptibility of iso- and cycloalkanes to methanogenic biodegradation by incubating them with mature fine tailings (MFT) collected from two depths (6 and 31 m below surface) of a tailings pond, representing different lengths of exposure to hydrocarbons. A mixture of five iso-alkanes and three cycloalkanes was incubated with MFT for 1700 d. Iso-alkanes were completely biodegraded in the order 3-methylhexane > 4-methylheptane > 2-methyloctane > 2-methylheptane, whereas 3-ethylhexane and ethylcyclopentane were only partially depleted and methylcyclohexane and ethylcyclohexane were not degraded during incubation. Pyrosequencing of 16S rRNA genes showed enrichment of Peptococcaceae (Desulfotomaculum) and Smithella in amended cultures with acetoclastic (Methanosaeta) and hydrogenotrophic methanogens (Methanoregula and Methanoculleus). Bioaugmentation of MFT by inoculation with MFT-derived enrichment cultures reduced the lag phase before onset of iso-alkane and cycloalkane degradation. However, the same enrichment culture incubated without MFT exhibited slower biodegradation kinetics and less CH₄ production, implying that the MFT solid phase (clay minerals) enhanced methanogenesis. These results help explain and predict continued emissions of CH₄ from oil sands tailings repositories in situ.

Ageing of various plastics in marine environment was monitored after immersion of two synthetic (polyvinylchloride, PVC, and polyethylene terephthalate, PET) and one biodegradable (poly(butylene adipate co-terephtalate), PBAT) plastics for 502days in the bay of Lorient (Brittany, France). Data analysis indicates that aged PVC rapidly releases estrogenic compounds in seawater with a later adsorption of heavy metals; PET undergoes a low weakening of the surface whereas no estrogenic activity is detected; PBAT ages faster in marine environment than PVC. Aged PBAT exhibits heterogeneous surface with some cavities likely containing clay minerals from the chlorite group. Besides, this degraded material occasionally shows a high estrogenic activity. Overall, this study reports, for the first time, that some aged plastics, without being cytotoxic, can release estrogenic compounds in marine environment.

The elevated concentration of arsenic (As) in the groundwaters of many countries worldwide has received much attention during recent decades. This article presents an overview of the natural geochemical processes that mobilize As from aquifer sediments into groundwater and provides a concise description of the distribution of As in different global groundwater systems, with an emphasis on the highly vulnerable regions of Southeast Asia, the USA, Latin America, and Europe. Natural biogeochemical processes and anthropogenic activities may lead to the contamination of groundwaters by increased As concentrations. The primary source of As in groundwater is predominantly natural (geogenic) and mobilized through complex biogeochemical interactions within various aquifer solids and water. Sulfide minerals such as arsenopyrite and As-substituted pyrite, as well as other sulfide minerals, are susceptible to oxidation in the near-surface environment and quantitatively release significant quantities of As in the sediments. The geochemistry of As generally is a function of its multiple oxidation states, speciation, and redox transformation. The reductive dissolution of As-bearing Fe(III) oxides and sulfide oxidation are the most common and significant geochemical triggers that release As from aquifer sediments into groundwaters. The mobilization of As in groundwater is controlled by adsorption onto metal oxyhydroxides and clay minerals. According to recent estimates, more than 130 million people worldwide potentially are exposed to As in drinking water at levels above the World Health Organization’s (WHO's) guideline value of 10 μg/L. Hence, community education to strengthen public awareness, the involvement and capacity building of local stakeholders in targeting As-safe aquifers, and direct action and implementation of best practices in identifying safe groundwater sources for the installation of safe drinking water wells through action and enforcement by local governments and international water sector professionals are urgent necessities for sustainable As mitigation on a global scale.

Unusually large amounts of marine snow, including Extracellular Polymeric Substances (EPS), were formed during the 2010 Deepwater Horizon oil spill. The marine snow settled with oil and clay minerals as an oily sludge layer on the deep sea floor. This study tested the hypothesis that the unprecedented amount of chemical dispersants applied during high phytoplankton densities in the Gulf of Mexico induced high EPS formation. Two marine phytoplankton species (Dunaliella tertiolecta and Phaeodactylum tricornutum) produced EPS within days when exposed to the dispersant Corexit 9500. Phytoplankton-associated bacteria were shown to be responsible for the formation. The EPS consisted of proteins and to lesser extent polysaccharides. This study reveals an unexpected consequence of the presence of phytoplankton. This emphasizes the need to test the action of dispersants under realistic field conditions, which may seriously alter the fate of oil in the environment via increased marine snow formation.