Nitrogen (N) addition can change physicochemical properties and biogeochemical processes in soil, but whether or not these changes further affect the transport and transformation of heavy metal speciation is unknown. Here, a long-term (2004–2016) field experiment was conducted to assess the responses of different heavy metal speciation in three soil aggregate fractions to N additions in a temperate agroecosystem of North China. The organic matter turnover time was quantified based on changes in δ13C following the conversion from C3 (wheat) to C4 crop (corn). Averagely, N addition decreases and increases the heavy metal contents in bioavailable and organic bound fractions by 27.5% and 16.6%, respectively, suggesting N addition promotes the transformation of heavy metal speciation from bioavailable to organic bound, and such a promotion in a small aggregate fraction is more remarkable than that in a large aggregate fraction. The transformations of heavy metal speciation from bioavailable to organic bound in all soil aggregate fractions are largely dependent on the increments in the turnover time of organic matter. The increase in organic matter turnover time induced by N addition may inhibit the desorption of heavy metals from organic matter by prolonging the interaction time between heavy metals and organic matter and enhance the capacity of organic matter to adsorb heavy metals by increasing the humification degree and functional group. Our work can provide insights into the accumulation, migration, and transformation of heavy metals in soils in the context of increasing global soil N input from a microenvironmental perspective.

Antibiotics in water and soil are persistent, bioaccumulative and toxic to aquatic organisms and human health. To address it, as one of the new technologies, green synthesized magnetic Fe₃O₄ nanoparticles by Excoecaria cochinchinensis extract used to remove rifampicin (RIF) was investigated in this study. Results showed the adsorption efficiency of RIF reached 98.4% and the maximum adsorption capacity is 84.8 mg/g when 20 mL of RIF at a concentration of 20 M was adsorbed by 10 mg Fe₃O₄ at a temperature of 303 K. The morphology of the green Fe₃O₄ characterized by SEM demonstrated the dimensions ranging from 20 to 30 nm. The N₂ adsorption/desorption isotherms revealed that the surface area of Fe₃O₄ was 111.8 m²/g. In addition, adsorption studies indicated that the kinetics fitted the pseudo second-order and isothermal adsorption conformed to the Langmuir isotherm. Furthermore, due to their magnetic properties, the Fe₃O₄ nanoparticles were easily separated and reused and the mechanism for removing RIF occurred through adsorption rather than chemical redox reaction. Finally, the reusability of Fe₃O₄ for adsorption of RIF showed that the removal efficiency decreased to 61.5% after five cycles.

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.

Sorption studies of organic pollutants by microplastics (MPs) in single-solute systems are well established in the literature. However, actual aquatic environments always contain a mixture of contaminants. Prediction of the fate and biological effects of MPs-mediated chemical exposure requires a better understanding of sorption-desorption processes of multiple organic contaminants by MPs. In this study, the altered sorption and desorption behaviors of individual organic UV filters (BP-3 and 4-MBC) in the presence of cosolutes (BP-3, 4-MBC, EHMC and OC) on two types of MPs (LDPE and PS) were examined. In most cases, co-occurrence of other organic UV filters appeared to have an antagonistic effect on the sorption of primary solute, which was consistent with trends found in previous studies. Nevertheless, the sorption uptake of 4-MBC as primary solute on PS was enhanced in the presence of cosolute(s), arising presumably from solute multilayer formation caused by laterally attractive π-π interactions between adsorbed cosolute(s) and 4-MBC molecules. Such formation of multilayer sorption in multi-solute systems depends on the solute hydrophobicity and concentration as well as inherent sorptivity of MPs. Our further desorption experiments revealed that the bioaccessibility of primary solute was significantly elevated with cosolutes, even though competitive sorption was observed under the same experimental conditions. These findings supplement the current knowledge on sorption mechanisms and interactions of multiple organic contaminants on MPs, which are critical for a comprehensive environmental risk assessment of both MPs and hazardous anthropogenic contaminants in natural environments.

The predominance of natural organic matter (NOM) in nonlinear sorption of nonionic organic compounds (NOCs) is a fundamental behavior that controlling the fate, transfer and bioavailability of NOCs in natural environment. There is a debate, i.e., whether the nonlinear sorption is captured by nonlinear partition mechanism or adsorption mechanism. The debate has been going on for decades because characteristics of nonlinear partition are still unknown due to the lack of an adsorbent that can partition NOCs nonlinearly. We find a resin ADS-21, with specific surface area undetectable (<0.5 m² g⁻¹) but high sorption capacity for NOCs (up to 1000 mg g⁻¹ for phenol as an example), is an ideal adsorbent for examining characteristics of nonlinear partitioning. This resin has nonlinear isotherms for phenols and anilines but linear isotherms for polycyclic aromatic hydrocarbons and nitrobenzenes. The observed positively linear relationship of sorption capacities of NOCs with NOCs solubility in water or octanol, could be one of the characteristics of nonlinear partition. Moreover, competitive sorption and no desorption hysteresis could be observed for the nonlinear partition. Hydrogen-bonding of phenols and anilines with ADS-21 is responsible for nonlinear partition, competitive sorption and isotherm nonlinearity. These evidences would be supportive for understanding nonlinear partition and the nonlinear sorption of NOCs by NOM.

Hydrophobic legacy contaminants like dichlorodiphenyltrichloroethane (DDT) and polychlorinated biphenyls (PCBs) were banned almost half a century ago. While their residues still remain in many environmental compartments, they have undergone extensive aging and likely have lower bioaccessibility (the available fraction) compared to fresh residues. However, risk assessment relies heavily on the use of total chemical concentration, rather than accounting for age-diminished bioaccessibility, likely leading to overestimated risks. In this study, we used 24 h Tenax desorption to measure the potential bioaccessibility of DDTs and PCBs in two sediment cores taken from the Palos Verdes Shelf Superfund site in the Pacific Ocean. The total concentrations of DDTs and PCBs from the core located at the sewage outfall (8C) were as high as 41,000–15,700 μg/kg (dry weight, dw) and 530-2600 μg/kg dw, respectively, while those from a location 7 km northeast of the outfall (3C) were 2–3 orders of magnitude lower. Bioaccessibility estimated by 24-h Tenax-aided desorption (F24h) decreased in the order of DDD > DDE > DDT for DDT derivatives, and PCB 52 > PCB 70 > PCB 153 for PCB congeners, showing a negative correlation with their log Kow. Due to the extensive aging, F24h values were <20% of the total chemical concentration for most contaminants and <5% for DDT, DDE and PCB 153, suggesting that aging greatly diminished their bioavailability. However, a quantitative relationship between F24h and sediment age along the vertical profile was not found, likely because the contaminant residues had undergone aging before their offsite transport and deposition onto the ocean floor. As the use of man-made chemicals such as DDT and PCBs was discontinued in the U.S. many decades ago, the reduction in their bioavailability due to aging may be universal and should be taken into consideration to avoid overly conservative risk predictions or unnecessary mitigation interventions.

Recent classification of metformin as an emerging contaminant warrants assessment of its fate and behaviour in the natural environment especially with land-based application of potentially contaminated wastewaters and biosolids. The present study provided further insight into the sorption mechanisms of metformin and its transformation product guanylurea in soil and upon biosolid fortification. Decreased metformin sorption (12.4%) as measured by the effective distribution coefficient (Kdᵉᶠᶠ) was observed with biosolids amendment while significant increase (2500%) in guanylurea sorption was calculated. Analysis of co-solute effects confirmed their contrasting sorption mechanisms with the absence of competitive effects in unamended soil. Results of the column tests were in good agreement with the batch sorption studies as the fitted values of retardation factors decreased and increased for metformin and guanylurea, respectively, upon addition of biosolids. The shapes of the breakthrough curves suggest slower desorption rates for both compounds in unamended soil resulting to non-equilibrium conditions and back-end tailings. However, in biosolid-amended soil columns, these tailings were less pronounced resembling equilibrium transport. Results also demonstrated enhanced mobility of both compounds upon biosolids fortification. The non-equilibrium chemical transport model fitted the measured data well (0.975 > r² > 0.988) especially for unamended soils which suggests the existence of non-equilibrium conditions and rate-limited sorption sites.

Elevated inorganic arsenic concentrations in groundwater has become a major public and environmental health concern in different parts of the world. Currently, As-contaminated groundwater issue in many countries and regions is a major topic for publications at global level. However, there are many regions worldwide where the problem has still not been resolved or fully understood due to inadequate hydrogeochemical investigations. Hence, this study evaluates for the first time the hydrogeochemical behavior of the arid and previously unexplored inland basin of Sirjan Plain, south east (SE) Iran, in order to assess the controlling factors which influence arsenic (As) mobility and its distribution through groundwater resources. Total inorganic arsenic concentration was measured using inductive-coupled plasma optical emission spectrometry (ICP-OES). Arsenic content in groundwater of this region ranged between 2.4 and 545.8 μg/L (mean value: 86.6 μg/L) and 50% of the samples exceeded the World Health Organization (WHO) guideline value of 10 μg/L in drinking water. Groundwater was mainly of Na-Cl type and alkaline due to silicate weathering, ion exchange and evaporation in arid conditions. Elevated As concentrations were generally observed under weakly alkaline to alkaline conditions (pH > 7.4). Multivariate statistical analysis including cluster analysis and bi-plot grouped As with pH and HCO3 and demonstrated that the secondary minerals including oxyhydroxides of Fe are the main source of As in groundwater in this region. The desorption of As from these mineral phases occurs under alkaline conditions in oxidizing arid environments thereby leading to high levels of As in groundwater. Moreover, evaporation, ion exchange and saltwater intrusion were the secondary processes accelerating As release and its mobility in groundwater. Based on the results of this study, desorption of As from metal oxy-hydroxides surfaces under alkaline conditions, evaporation and intrusion of As-rich saline water are considered to be the major factors causing As enrichment in arid inland basins such as those in southeast Iran. This study proposes the regular monitoring and proper groundwater management practices to mitigate high levels of arsenic in groundwater and related drinking water wells of Sirjan Plain.

Marine polychaetes and fish are known to ingest polystyrene microparticles in the environment. Laboratory microplastic feeding experiments have demonstrated that plastic may release endocrine-disrupting compounds such as diethylhexyl phthalate (DEHP), which can cause adverse effects in both vertebrates and invertebrates. In order to determine the influence of size and digestive conditions on the desorption of DEHP and other plasticizers to polychaetes and fish, we exposed polystyrene particles of various sizes under invertebrate and vertebrate digestive conditions (vertebrate mimic; pepsin, pH = 2.0, 24 °C, invertebrate mimic; Na taurocholate pH = 7, 18 °C). Estrogen receptor activation and concentrations of 12 plasticizers were measured in the extracts. DEHP, bisphenol S and 4-tert-octylphenol were the only compounds detected. Simulated vertebrate gut digestion did not significantly enhance the release of chemicals nor estrogenic activity. However, a 6.3 ± 2.0-fold increase in the concentration of DEHP was observed in extracts from invertebrate gut conditions (Mean ± SD; N = 24, p < 0.0001). Additionally, estimated particle surface area was positively correlated with estrogenic activity across all treatment types (r = 0.85, p < 0.0001). Overall, these data indicate an elevated bioaccessibility of DEHP may occur in invertebrates, and size-dependent desorption of uncharacterized estrogenic compounds from plastic suggest additional complexity when considering the risks of MP to aquatic organisms.

Dissolved organic carbon (DOC) has a major influence upon sorption/desorption and transport of hydrophobic organic contaminants (HOCs) in soil environments. However, the molecular mechanisms of DOC sorption and its effects on aged HOC desorption in contaminated soils still remain largely unclear. Here, effects of three different DOC (one from commercial peat and two from biochars produced at 300 °C and 500 °C pyrolysis temperatures, respectively) and oxalate (as a reference) on abiotic desorption behavior of aged phenanthrene from three agricultural soils were investigated. Results showed that desorption of aged phenanthrene from soils was predominantly dependent on soil organic carbon content. The presence of DOC and oxalate resulted in higher desorption of phenanthrene compared to water alone, and the effects were positively related to soil organic carbon content and DOC/oxalate concentration. The facilitating effects of DOC were further increased during the second consecutive desorption, whereas oxalate had no such effect. Ultra-high-resolution Fourier transform-ion cyclotron resonance-mass spectrometry confirmed the molecular fractionation of DOC at the soil-water interface during DOC sorption. Specifically, the DOC molecules with O-rich moieties were preferentially adsorbed, whereas the molecules with phenolic and aromatic structures were selectively retained in the soil solutions through competitive displacement and co-sorption reactions during sorption. The enriched phenyl structures in the retained DOC facilitated its association with phenanthrene in the solutions and thus the release of phenanthrene from the soils. In contrast, oxalate replaced some organic carbon from the soils and thus released the associated phenanthrene into the solutions. Our findings highlight the importance of the molecular composition and structure of DOC for the desorption of phenanthrene in soil-water environments, which may help improve our understanding of the release and transport of organic compounds in the environments.