Freshwater salinization is a rapidly emerging ecological issue and is correlated with significant declines in aquatic biodiversity. It remains unclear how changing salinity regimes affect the physiology of sensitive aquatic insects. We used the parthenogenetic mayfly, Neocloeon triangulifer, to ask how ionic exposure history alters physiological processes and responses to subsequent major ion exposures. Using radiotracers (²²Na, ³⁵SO₄, and ⁴⁵Ca), we observed that mayflies chronically reared in elevated sodium or sulfate (157 mg L⁻¹ Na or 667 mg L⁻¹ SO₄) had 2-fold (p < 0.0001) and 8-fold (p < 0.0001) lower ion uptake rates than mayflies reared in dilute control water (16 mg L⁻¹ Na and 23 mg L⁻¹ SO₄) and subsequently transferred to elevated salinities, respectively. These acclimatory ion transport changes provided protection in 96-h toxicity bioassays for sodium, but not sulfate. Interestingly, calcium uptake was uniformly much lower and minimally influenced by exposure history, but was poorly tolerated in the toxicity bioassays. With qRT-PCR, we observed that the expression of many ion transporter genes in mayflies was influenced by elevated salinity in an ion-specific manner (general upregulation in response to sulfate, downregulation in response to calcium). Elevated sodium exposure had minimal influence on the same genes. Finally, we provide novel light microscopic evidence of histomorphological changes within the epithelium of the Malpighian tubules (insect primary excretory system) that undergoes cellular degeneration and necrosis secondary to calcium toxicity. We conclude that physiological plasticity to salinity stress is ion-specific and provide evidence for ion-specific toxicity mechanisms in N. triangulifer.

Private wells in Ireland and elsewhere have been shown to be prone to microbial contamination with the main suspected sources being practices associated with agriculture and domestic wastewater treatment systems (DWWTS). While the microbial quality of private well water is commonly assessed using faecal indicator bacteria, such as Escherichia coli, such organisms are not usually source-specific, and hence cannot definitively conclude the exact origin of the contamination. This research assessed a range of different chemical contamination fingerprinting techniques (ionic ratios, artificial sweeteners, caffeine, fluorescent whitening compounds, faecal sterol profiles and pharmaceuticals) as to their use to apportion contamination of private wells between human wastewater and animal husbandry wastes in rural areas of Ireland. A one-off sampling and analysis campaign of 212 private wells found that 15% were contaminated with E. coli. More extensive monitoring of 24 selected wells found 58% to be contaminated with E. coli on at least one occasion over a 14-month period. The application of fingerprinting techniques to these monitored wells found that the use of chloride/bromide and potassium/sodium ratios is a useful low-cost fingerprinting technique capable of identifying impacts from human wastewater and organic agricultural contamination, respectively. The artificial sweetener acesulfame was detected on several occasions in a number of monitored wells, indicating its conservative nature and potential use as a fingerprinting technique for human wastewater. However, neither fluorescent whitening compounds nor caffeine were detected in any wells, and faecal sterol profiles proved inconclusive, suggesting limited suitability for the conditions investigated.

The present study was aimed at investigating the effects of different acids and pH neutralizers applied to dredged marine sediment for the treatment of heavy metals, and the resulting influence on the sediment quality as a plant growth medium. The inspection of barley germination in the dredged marine sediment revealed that residual salts are critical plant stressors whose adverse effects exceed those exhibited by high-level heavy metals and petroleum hydrocarbons present in the sediment. Acid washing and pH neutralization reduced not only the heavy metal contents but also the sediment salinity (by factors of 6.1–9.5), resulting in 100% germination of barley. For acid-washed and calcium-oxide-neutralized sediment, the barley growth was comparable to that observed in untreated and water washed sediment despite factors of 5.2–8.0 greater sediment salinity in the former. This result represents the protective effect of residual calcium against sodium and chloride toxicity. Water washing of acid-washed and pH-neutralized sediments further enhanced barley growth owing to the reduction in osmotic pressure. This study showed the effect of different sediment-washing reagents on the product quality. It also indicated the significance of balancing the enhancement of product quality and economic cost of further treatment requirements.

Chemically oxidative removal of polycyclic aromatic hydrocarbons (PAHs) in soil is related to their occurrence state. Whether the heterogeneity of natural organic matter has an effect on the occurrence of PAHs in soil and, if there is an effect, on the oxidative removal efficiency of PAHs remains unknown. In this study, the removal efficiencies of 16 priority PAHs aged in humic acids (HAs) of different soil aggregate fractions by various oxidants were investigated by combining soil fractionation and microreaction experiments. Results showed that the accumulations of PAHs in particulate HA (P-HA) and microaggregate occluded HA (MO-HA) mainly occurred in the early period of the aging time frame. In contrast, PAH accumulation in non-aggregated silt and clay associated HA (NASCA-HA) was relatively slow and tended to saturate in the late period of the aging time frame. The cumulative contents of PAHs throughout the entire aging period in MO-HA and NASCA-HA were significantly greater than that in P-HA. The aged PAHs in P-HA and NASCA-HA exhibited the highest and lowest removal efficiencies, respectively. This ranking was mainly governed by the molecular size and polarity of HAs. Sodium persulfate and potassium permanganate had the highest removal efficiencies in total PAHs in HAs, with average efficiencies of 85.8% and 79.1%, respectively, in P-HA. Hydrogen peroxide had the lowest degradation efficiency in PAHs. In particular, the degradation efficiency of total PAHs in NASCA-HA was lowered to 31.0%. PAH congeners in HAs showed a large difference in oxidative removal efficiency. Low-ring PAH was more easily degraded than medium- and high-ring PAHs, and in most treatments, fluoranthene and pyrene in the medium ring and benzo[a]pyrene in the high ring demonstrated higher efficiencies than other PAHs with the same number of rings. Our findings are useful in promoting the accurate and green remediation of PAH-contaminated soils.

Bitumen recovery from oil sands in northeastern Alberta, Canada produces large volumes of tailings, which are deposited in mining areas that must be reclaimed upon mine closure. A new technology of non-segregated tailings (NST) developed by Canadian Natural Resources Limited (CNRL) was designed to accelerate the process of oil sands fine tailings consolidation. However, effects of these novel tailings on plants used for the reclamation of oil sands mining areas remain to be determined. In the present study, we investigated the effects of NST on seedlings of three species of plants commonly planted in oil sands reclamation sites including paper birch (Betula papyrifera), white spruce (Picea glauca) and green alder (Alnus viridis). In the controlled-environment study, we grew seedlings directly in NST and in the two types of reclamation soils with and without added NST and we measured seedling growth, gas exchange parameters, as well as tissue concentrations of selected elements and foliar chlorophyll. White spruce seedlings suffered from severe mortality when grown directly in NST and their needles contained high concentrations of Na. The growth and physiological processes were also inhibited by NST in green alder and paper birch. However, the addition of top soil and peat mineral soil mix to NST significantly improved the growth of plants, possibly due to a more balanced nutrient uptake. It appears that NST may offer some advantages in terms of site revegetation compared with the traditional oil sands tailings that were used in the past. The results also suggest that, white spruce may be less suitable for planting at reclamation sites containing NST compared with the two studied deciduous tree species.

The increasing production and use of graphene-based nanomaterials (e.g., graphene oxide (GO) and reduced graphene oxide (RGO)) will lead to their environmental release. To date, transport of RGOs in saturated porous media is poorly understood. Here, we examined the transport behaviors of three RGO materials obtained by reducing a GO product with commonly used reducing agents – N₂H₄, NaBH₄ and L-ascorbic acid (referred to as N₂H₄-RGO, NaBH₄-RGO and VC-RGO, respectively). When the dominant background cation was Na⁺, K⁺ or Mg²⁺, the mobility of the RGOs and GO in saturated quartz sand correlated well with their surface C/O ratio. Interestingly, the lower mobility of the more reduced materials (the ones with higher C/O values) was not only the results of their less negative surface charges and larger particle sizes, but also the outcome of their greater hydrophobicity, in line with the calculated extended Derjaguin–Landau–Verwey–Overbeek (XDLVO) profiles. Counterintuitively, when the background cation was Ca²⁺, the least reduced material among the three RGOs, VC-RGO, exhibited the lowest mobility. Analysis of electrophoretic and aggregation properties, as well as pH-effect experiments, indicated that the surprisingly low mobility of VC-RGO was attributable to the strong cation-bridging effect (primarily Ca²⁺-bridging between RGO and quartz sand) associated with this material, as VC-RGO contained the highest amount of surface carboxyl group (a strong metal-binding moiety). Notably, enhanced attachment (due to increased hydrophobic effect and cation-bridging) and particle aggregation appeared to work synergistically to increase RGO retention, as the attachment of large RGO aggregates significantly enhanced particle straining by narrowing the flow path. These observations reveal a largely overlooked link between the mobility of graphene-based materials and their key physicochemical properties.

The present study aims to investigate the spatial distribution and associated various geochemical mechanisms responsible for fluoride (F⁻) contamination in groundwater of unconfined aquifer system along major rivers in Sindh and Punjab, Pakistan. The concentration of F⁻ in groundwater samples ranged from 0.1 to 3.9 mg/L (mean = 1.0 mg/L) in Sindh and 0.1–10.3 mg/L (mean = 1.0 mg/L) in Punjab, respectively with 28.9% and 26.6% of samples exhibited F⁻ contamination beyond WHO permissible limit value (1.5 mg/L). The geochemical processes regulated F⁻ concentration in unconfined aquifer mainly in Sindh and Punjab were categorized as follows: 1) minerals weathering that observed as the key process to control groundwater chemistry in the study areas, 2) the strong correlation between F⁻ and alkaline pH, which provided favorable environmental conditions to promote F⁻ leaching through desperation or by ion exchange process, 3) the 72.6% of samples from Sindh and Punjab were dominated by Na⁺- Cl⁻ type of water, confirmed that the halite dissolution process was the major contributor for F⁻ enrichment in groundwater, 4) dolomite dissolution was main process frequently observed in Sindh, compared with Punjab, 5) the arid climatic conditions promote evaporation process or dissolution of evaporites or both were contributing to the formation of saline groundwater in the study area, 6) the positive correlation observed between elevated F⁻ and fluorite also suggested that the fluorite dissolution also played significant role for leaching of F⁻ in groundwater from sediments, and 7) calcite controlled Ca2⁺ level and enhanced the dissolution of F-bearing minerals and drive F⁻ concentration in groundwater. In a nut shell, this study revealed the worst scenarios of F⁻ contamination via various possible geochemical mechanisms in groundwater along major rivers in Sindh and Punjab, Pakistan, which need immediate attention of regulatory authorities to avoid future hazardous implications.

Constructed wetlands are an environmentally friendly and economically efficient sewage treatment technology, with fillers playing an important role in treatment processes. However, traditional wetland fillers (e.g. zeolite) are known to be imperfect because of their low adsorption capacity. In this paper, the adsorbent sodium titanate nano fillers (T3-F) was synthesized as an alternative to traditional filler with sodium titanate nanofibers (T3) as the raw material, epoxy adhesive as the adhesive agent and NH₄HCO₃ as the pore-making agent. The properties of T3-F were characterized by powder X-ray diffraction (XRD), scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDX), porosity. The effect of different parameters such as pH, co-existing ions, contact time, initial metal ion concentrations and temperature was investigated for heavy metal adsorption. The results showed that the adsorption of heavy metal by T3-F followed the pseudo-second-order kinetic and Langmuir isotherm models. The maximum adsorption capacities for Cu²⁺, Pb²⁺, Zn²⁺, Cd²⁺ were about 1.5–1.98 mmol/g, which were 4–5 times that of zeolite, the traditional commonly used filler. Moreover, T3-F could entrap toxic ions irreversibly and maintain structural stability in the adsorption process, which solved the issue of secondary pollution. In the presence of competing ions, the adsorption efficiency for Pb²⁺ was not reduced significantly. Adsorption was strongest at high pH. From the results and characterization, an adsorption mechanism was suggested. This study lays a foundation for the practical application of T3-F as a constructed wetland filler in the future.