Distribution in ice is regarded as one of important transport modes for pollutants in seasonal freeze-up waters in cold regions. However, the distribution characteristics and mechanisms of fluorinated antibiotics as emerging contaminants during the water freezing process remain unclear. Here, florfenicol and norfloxacin were selected as model fluorinated antibiotics to investigate their ice-water distribution. Effects of antibiotic molecular structure on the distribution were explored through comparative studies with their non-fluorinated structural analogs. Results showed that phase changes during the ice growth process redistributed the antibiotics, with antibiotic concentrations in water 3.0–6.4 times higher than those in ice. The solute-rich boundary layer with a concentration gradient was presented at the ice-water interface and controlled by constitutional supercooling during the freezing process. The ice-water distribution coefficient (KIW) values of antibiotics increased by 34.8%–38.0% with a doubling of the cooling area. The solute distribution coefficient (Kbₛ) values of antibiotics at −20 °C were 65.6%–70.3% higher than at −10 °C. The KIW and Kbₛ values of all antibiotics were negatively correlated with their water solubilities. The fluorine substituents influenced the binding energies between antibiotics and ice, resulting in a 1.1-fold increase in the binding energy of norfloxacin on the ice surface relative to its structural analog pipemidic acid. The results provide a new insight into the transport behaviors of fluorinated pharmaceuticals in ice-water systems.

The m-aminophenol (m-AP) is a widely used industrial chemical, which enters water, soils, and sediments with waste emissions. A common soil metal oxide, birnessite (δ-MnO2), was found to mediate the transformation of m-AP with fast rates under acidic conditions. Because of the highly complexity of the m-AP transformation, mechanism-based models were taken to fit the transformation kinetic process of m-AP. The results indicated that the transformation of m-AP with δ-MnO2 could be described by precursor complex formation rate-limiting model. The oxidative transformation of m-AP on the surface of δ-MnO2 was highly dependent on reactant concentrations, pH, temperature, and other co-solutes. The UV-VIS absorbance and mass spectra analysis indicated that the pathway leading to m-AP transformation may be the polymerization through the coupling reaction. The m-AP radicals were likely to be coupled by the covalent bonding between unsubstituted C2, C4 or C6 atoms in the m-AP aromatic rings to form oligomers as revealed by the results of activation energy and mass spectra. Furthermore, the toxicity assessment of the transformation productions indicated that the toxicity of m-AP to the E. coli K-12 could be reduced by MnO2 mediated transformation. The results are helpful for understanding the environmental behavior and potential risk of m-AP in natural environment.

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.

Measurement of solute-transport parameters through soils for a wide range of solute- and soil-types is time-consuming, laborious, expensive and practically impossible. So, indirect methods for estimating the transport parameters by pedo-transfer functions are now advancing. This study developed and evaluated an Artificial Neural Network (ANN) model for estimating the transport velocity (V), dispersion coefficient (D) and retardation factor (R) of NaAsO₂, Pb(NO₃)₂, Cd(NO₃)₂, C₉H₉N₃O₂ and CaCl₂ from the basic soil properties. Breakthrough data of the solutes were measured in 14 agricultural soils of Bangladesh by time-domain reflectometry (TDR) in repacked soil columns under unsaturated steady-state water-flow conditions. The transport parameters of the chemicals were determined by analyzing the solute breakthrough data. Bulk density (γ), organic carbon (OC), clay (C) content, pH, median grain diameter (D₅₀) and uniformity coefficient (Cᵤ) of the soils were determined. An ANN model for V, D and R was developed by using data of eight soils, validated/tested with the data of five soils and verified with the data of one soil. Clay content and bulk density of the soils were the most sensitive input variables to the ANN model followed by other soil properties (OC, C, pH, D₅₀ and Cᵤ). The model reliably predicted V, D and R with relative root-mean-square error (RRMSE) of 0.028–0.363, mean error (ME) of – 0.00004 to 0.0005, bias error (BOE%) of 0–0.003 and modeling efficiency (EF) of >0.99. Thus, the ANN model can significantly enhance prediction of pollution transport through soils in terms of cost and effort.

Overburden and tailings materials from oil sands production were used as construction materials as part of a novel attempt to create a self-sustaining, peat accumulating fen-upland ecosystem. To evaluate the potential for elemental release from the construction materials, total elemental concentrations in the tailings sand, petroleum coke and peat used to construct a fen ecosystem were determined using microwave-assisted acid digestions and compared to a leaching experiment conducted under environmentally-relevant conditions. A comparison of solid phase to aqueous Na, Ca, S and Mg concentrations showed they were highly leachable in the materials. Given that the concentrations of these elements can affect plant community structure, it is important to understand their leachability and mobility as they migrate between materials used to construct the system. To that end, a mass balance of aqueous Na, Ca, S and Mg was conducted based on leaching experiments and materials analysis coupled with existing data from the constructed system. The data indicate that there is a large pool of leachable Na, Ca, S and Mg in the system, estimated at 27 t of Na, 14 t of Ca, 37.3 t of S and 8.8 t of Mg. Since recharge mainly drives the fen-upland system water regime, and discharge in the fen, evapo-accumulation of these solutes on the surface may occur.

This study aimed to investigate the difference of osmoregulation between two edible amaranth cultivars, Liuye (high Cd accumulator) and Quanhong (low Cd accumulator), under salinity stress and determine the effects of such difference on Cd accumulation. A pot experiment was conducted to expose the plants to sewage-irrigated garden soil (mean 2.28 mg kg⁻¹ Cd) pretreated at three salinity levels. Under salinity stress, the concentrations of Cd in the two cultivars were significantly elevated compared with those in the controls, and the Cd concentration in Liuye was statistically higher than that in Quanhong (p < 0.05). Salinity-induced osmoregulation triggered different biogeochemical processes involved in Cd mobilization in the rhizosphere soil, Cd absorption, and translocation by the two cultivars. Rhizosphere acidification induced by an imbalance of cation over anion uptake was more serious in Liuye than in Quanhong, which obviously increased soil Cd bioavailability. Salinity-induced injuries in the cell wall pectin and membrane structure were worse in Liuye than in Quanhong, increasing the risk of Cd entering the protoplasts. The chelation of more cytoplasmic Cd²⁺ with Cl⁻ ions in the roots of Liuye promoted Cd translocation into the shoots. Furthermore, the less organic solutes in the root sap of Liuye than in that of Quanhong also favored Cd translocation into the shoots. Hence, osmoregulation processes can be regarded as important factors in reducing Cd accumulation in crop cultivars grown on saline soils.

In reverse osmosis, a frequently used technology in water desalination processes, wastewater (RO concentrate) is generated containing the retained solutes as well as so-called antiscalants (AS), i.e. chemical substances that are commonly applied to prevent membrane-blocking. In this study, a risk assessment of a possible discharge of concentrate into a small stream was conducted. The acute toxicity of two concentrates containing two different ASs and of concentrate without AS to the amphipods Gammarus pulex and Gammarus roeseli was studied. Mortality of gammarids exposed to the concentrate without AS was not different to the control, whereas concentrates including ASs caused mortality rates up to 100% at the highest test concentrations after 168 h. Resulting EC50-values were 36.2–39.4% (v/v) after 96 h and 26.6–58.0% (v/v) after 168 h. These results suggest that the ecotoxicological relevance of antiscalants is greater than currently assumed.

Shale was thermally treated to obtain a series of kerogen with varied maturation. Their chemical, structural and porous properties were related to the sorption and/or desorption behaviors of phenanthrene and benzene. As the treatment temperature increases, aliphatic and carbonyl carbon of the kerogen samples decrease, while their aromaticity and maturation increase. Meanwhile, the isothermal nonlinearity of phenanthrene and benzene increases whereas the sorption capacity and micropore adsorption volumes (Vo,d) initially increase and then decrease. The Vo,d of benzene is significantly correlated with, but higher than that of phenanthrene, suggesting similar micropore filling mechanism and molecular sieve effect. The benzene desorption exhibits hysteresis, which is related to the pore deformation of the kerogen and the entrapment of solute in the kerogen matrix. The Vo,d of phenanthrene and benzene on the kerogen samples accounts for 23–46% and 36–65% of the maximum sorption volumes, respectively, displaying the importance of the micropore filling.

A quantitative knowledge of the fate of deicing chemicals in the subsurface can be provided by joint analysis of lab experiments with numerical simulation models. In the present study, published experimental data of microbial degradation of the deicing chemical propylene glycol (PG) under flow conditions in soil columns were simulated inversely to receive the parameters of degradation. We evaluated different scenarios of an advection-dispersion model including different terms for degradation, such as zero order, first order and inclusion of a growing and decaying biomass for their ability to explain the data. The general break-through behavior of propylene glycol in soil columns can be simulated well using a coupled model of solute transport and degradation with growth and decay of biomass. The susceptibility of the model to non-unique solutions was investigated using systematical forward and inverse simulations. We found that the model tends to equifinal solutions under certain conditions.

We investigated the environmental impact of a deep water fish farm (190 m). Despite deep water and low water currents, sediments underneath the farm were heavily enriched with organic matter, resulting in stimulated biogeochemical cycling. During the first 7 months of the production cycle benthic fluxes were stimulated >29 times for CO₂ and O₂ and >2000 times for NH₄ ⁺, when compared to the reference site. During the final 11 months, however, benthic fluxes decreased despite increasing sedimentation. Investigations of microbial mineralization revealed that the sediment metabolic capacity was exceeded, which resulted in inhibited microbial mineralization due to negative feed-backs from accumulation of various solutes in pore water. Conclusions are that (1) deep water sediments at 8 °C can metabolize fish farm waste corresponding to 407 and 29 mmol m⁻² d⁻¹ POC and TN, respectively, and (2) siting fish farms at deep water sites is not a universal solution for reducing benthic impacts.