Urban stormwater is a major source of chemical pollution to receiving waters. Anthropogenic materials in the built environment can be an important source of chemicals to stormwater runoff. Roofing materials can leach significant amounts of metals, which vary over the life of the roof. We report concentrations of three metals (As, Cu, Zn) leaching into runoff from experimental panels of 14 roofing materials over 4.5 years of weathering. Ten roofing materials leached metals. Several leached >10 ppb during one or more study periods. The most common correlate with metal concentration was panel age, followed by precipitation amount. Extrapolating from these observations, we estimated the loading of metals from each roofing material during the first 10 years following installation. Eight materials were predicted to leach metals above background at the end of the 10 years. In combination with information on the prevalence of different roofing materials in the Puget Sound region of the Pacific Northwest, we estimated the relative amount of metals contributed from roofing materials in this basin. Most arsenic and copper was estimated to be contributed by residential roofing; nearly all arsenic from wood shakes manufactured with copper chromated arsenic, and copper contributed mainly from treated wood shakes followed by copper granule-containing asphalt shingles. Most zinc was estimated to be contributed by commercial roofs, including Zincalume and painted metal roofs. Overall our data shows that roofing materials can be an important long-term source of As, Cu, and Zn to stormwater runoff. Compared with atmospheric deposition, roof materials were a significant source, particularly of As and Cu. To get a complete picture of metals sourced from buildings, there is a need to study whole roof systems, including gutters, downspouts, and HVAC systems, as well as metals contributed from homeowner-applied treatments to their roofs.

The impact of commonly-used livestock antibiotics on soil nitrogen transformations under varying redox conditions is largely unknown. Soil column incubations were conducted using three livestock antibiotics (monensin, lincomycin and sulfamethazine) to better understand the fate of the antibiotics, their effect on nitrogen transformation, and their impact on soil microbial communities under aerobic, anoxic, and denitrifying conditions. While monensin was not recovered in the effluent, lincomycin and sulfamethazine concentrations decreased slightly during transport through the columns. Sorption, and to a limited extent degradation, are likely to be the primary processes leading to antibiotic attenuation during leaching. Antibiotics also affected microbial respiration and clearly impacted nitrogen transformation. The occurrence of the three antibiotics as a mixture, as well as the occurrence of lincomycin alone affected, by inhibiting any nitrite reduction, the denitrification process. Discontinuing antibiotics additions restored microbial denitrification. Metagenomic analysis indicated that Proteobacteria, Bacteroidetes, Actinobacteria, and Chloroflexi were the predominant phyla observed throughout the study. Results suggested that episodic occurrence of antibiotics led to a temporal change in microbial community composition in the upper portion of the columns while only transient changes occurred in the lower portion. Thus, the occurrence of high concentrations of veterinary antibiotic residues could impact nitrogen cycling in soils receiving wastewater runoff or manure applications with potential longer-term microbial community changes possible at higher antibiotic concentrations.

Plastic waste is continuously introduced not only into marine, but also freshwater environments, where it fragments into microplastics. Organisms may be affected by the particles themselves due to ingestion and indirectly via incorporated additives such as plasticizers, since these substances have the ability to leach out of the polymer matrix. Although it has been indicated that the likelihood of additives leaching out into the gut lumen of organisms exposed to microplastics is low, studies distinguishing between the effects of the synthetic polymer itself and incorporated additives of the same polymer are scarce. Since this is obligatory for risk assessment, we analyzed the chronic effects of flexible polyvinylchloride (PVC), a widely used polymer, containing the plasticizer diisononylphthalate (DiNP) on morphology and life history of the freshwater crustacean Daphnia magna and compared these effects with the effects of rigid PVC, lacking DiNP, as well as a glass bead control. After up to 31 days of exposure, rigid PVC and glass beads did not affect body length and relative tail spine length of D. magna, whereas flexible PVC led to an increased body length and a reduced number of offspring. None of the treatments increased the mortality significantly. We were able to show that 2.67μg/L DiNP leached out of the flexible PVC into the surrounding medium using GC-MS. Yet, we were not able to measure leachate inside the gut lumen of D. magna. The effects emerged towards the end of the experiment, due to the time dependent process of leaching. Therefore, the results highlight the relevance of long-term chronic exposure experiments, especially as leaching of additives takes time. Further, our study shows the importance to distinguish between microplastics containing leachable additives and the raw polymer in ecotoxicological testing.

This study developed a novel Hg(II) immobilization strategy by firstly incubating algal cells in high-phosphate cultures for surface modification, followed by obtaining the P-rich biomass as adsorbents for enhanced Hg(II) removal and then charring the Hg-loaded biomass to prevent leaching of phosphate and to immobilize Hg(II). For algal surface modification, Scenedesmus obtusus XJ-15 were cultivated under different P concentrations and obtained the highest sites concentration of surface phosphoryl functional groups in 80 mg L⁻¹ P cultures. For Hg(II) adsorption, biomass from 80 mg L⁻¹ P cultures (B-80) achieved the highest saturated sorption capacity of 95 mg g⁻¹ fitting to Langmuir isotherm model under the optimum pH of 5.0. For charring stabilization, the Hg-loaded B-80 was calcinated under different temperatures, and the product obtained from 300 °C charring showed the lowest Hg(II) leaching rate without P release. Moreover, FT-IR and XPS analysis indicate that the surge of surface phosphoryl functional groups dominated the enhancement of Hg(II) sorption and also Hg(II) charring immobilization. The above results suggested that the developed strategy is promising for both phosphate and mercury removal from water and for co-immobilization of P and Hg(II) to prevent leaching.

Usage of neonicotinoids is common in all agricultural regions of the world but data on environmental contamination in tropical regions is scarce. We conducted a survey of five neonicotinoids in soil, water and sediment samples along gradients from crops fields to protected lowland tropical forest, mangroves and wetlands in northern Belize, a region of high biodiversity value. Neonicotinoid frequency of detection and concentrations were highest in soil (68%) and lowest in water (12%). Imidacloprid was the most common residue reaching a maximum of 17.1 ng/g in soil samples. Concentrations in soils differed among crop types, being highest in melon fields and lowest in banana and sugarcane fields. Residues in soil declined with distance to the planted fields, with clothianidin being detected at 100 m and imidacloprid at more than 10 km from the nearest applied field. About half (47%) of the sediments collected contained residues of at least one compound up to 10 km from the source. Total neonicotinoid concentrations in sediments (range 0.014–0.348 ng/g d. w.) were about 10 times lower than in soils from the fields, with imidacloprid being the highest (0.175 ng/g). A probabilistic risk assessment of the residues in the aquatic environment indicates that 31% of sediment samples pose a risk to invertebrate aquatic and benthic organisms by chronic exposure, whereas less than 5% of sediment samples may incur a risk by acute exposure. Current residue levels in water samples do not appear to pose risks to the aquatic fauna. Fugacity modeling of the four main compounds detected suggest that most of the dissipation from the agricultural fields occurs via runoff and leaching through the porous soils of this region. We call for better monitoring of pesticide contamination and invertebrate inventories and finding alternatives to the use of neonicotinoids in agriculture.

CuFeO₂/CeO₂ as a novel catalyst was synthesized and its catalytic performance was evaluated for electro-Fenton degradation of acid orange 7 (AO7). It was demonstrated from the characterization results that the rhombohedral structure of CuFeO₂ and face-centered cubic fluorite structure of CeO₂ remained stable after nanocomposite construction. The impact of such operating parameters as pH, current intensity and, catalyst amount was investigated and the optimum conditions (100 mgL⁻¹ AO7, pH 3, 150 mgL⁻¹ CuFeO₂/CeO₂, I: 150 mA) determination led to 99.3% AO7 removal and 79.1% COD removal in 60 min. The introduction of CeO₂ as non-inert support had a significant impact on H₂O₂ electro-generation as an important step in AO7 removal. CuFeO₂/CeO₂ presented negligible metal leaching (iron 4.13%, copper 2.4%, and cerium 0.33%) which could be due to the strong interaction between active species and support. The nanocomposite performed efficiently in salty systems and two samples of real wastewaters due to Brønsted acidity character of ceria, which makes it a potential choice in industrial applications. The good performance of nanocomposite could be the result of the synergistic effect between Fe, Cu, and Ce. Regarding scavenging measurements results, the electro-Fenton process followed the Haber-Weiss mechanism. The by-products detection was performed using GC-MS analysis to propose an acceptable pathway for EF degradation of AO7. The BMG kinetics model (1/b = 0.969 (min) and 1/m = 0.269 (min⁻¹)) was matched with the experimental data and described the kinetics of reaction very well. The catalytic activity of CuFeO₂/CeO₂ almost remained after six cycles. Based on the obtained results, CuFeO₂/CeO₂ using the benefit of the synergistic effect of Ce³⁺ with Fe²⁺ and Cu⁺can be introduced as a promising novel catalyst for the electro-Fenton reaction in wastewater treatment.

Remediation of hexavalent chromium [Cr(VI)] has been widely studied for its high mobility and toxicity. As Cr(VI) migrates in natural environment, both soils and groundwater are contaminated simultaneously. In the present study, a novel reactor combining adsorption and microbial fuel cell (A-MFC) using Platanus acerifolia leaves was developed for removing Cr(VI) from groundwater and soils. When initial Cr(VI) concentration was 50 mg/L, the adsorption efficiency of A-MFC achieved 98% after 16 h. Afterwards, the leaves were used for fabricating an MFC-integrated leaching reactor. The A-MFC significantly improved the overall Cr(VI) removal efficiency through leaching and 40% of Cr(VI) in the soil column was removed. The electrical voltage and current of A-MFC reactor achieved averagely 343 mV and 141 μA to maintain the system operation without extra energy supply. This novel A-MFC reactor is an environmentally friendly technology which achieved efficient Cr(VI) removal from groundwater and soils using natural materials, proving the concept that integrated self-remediation of Cr(VI) in contaminated soil and groundwater with natural material and energy.

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.

In this study, a proposed integrated high-gravity technology for air pollution control, CO2 capture, and alkaline waste utilization was comprehensively evaluated from engineering, environmental, and economic perspectives. After high-gravity technology and coal fly ash (CFA) leaching processes were integrated, flue gas air emissions removal (e.g., sulfate dioxide (SO2), nitrogen oxides (NOx), total suspended particulates (TSP)) and CO2 capture were studied. The CFA, which contains calcium oxide and thus, had high alkalinity, was used as an absorbent in removing air pollution residues. To elucidate the availability of technology for pilot-scale high-gravity processes, the engineering performance, environmental impact, and economic cost were simultaneously investigated. The results indicated that the maximal CO2, SO2, NOx, and TSP removal efficiencies of 96.3 ± 2.1%, 99.4 ± 0.3%, 95.9 ± 2.1%, and 83.4 ± 2.6% were respectively achieved. Moreover, a 112 kWh/t-CO2 energy consumption for a high-gravity process was evaluated, with capture capacities of 510 kg CO2 and 0.468 kg NOx per day. In addition, the fresh, water-treated, acid-treated, and carbonated CFA was utilized as supplementary cementitious materials in the blended cement mortar. The workability, durability, and compressive strength of 5% carbonated CFA blended into cement mortar showed superior performance, i.e., 53 MPa ±2.5 MPa at 56 days. Furthermore, a higher engineering performance with a lower environmental impact and lower economic cost could potentially be evaluated to determine the best available operating condition of the high-gravity process for air pollution reduction, CO2 capture, and waste utilization.

Knowledge of the transport and fate of pathogenic Escherichia coli, especially in the areas contaminated with crude oil, is required to assess contamination of shallow groundwater resources. The present study aims to investigate the effect of crude oil-mediated water repellency on the movement of nalidixic acid-resistant Escherichia coli strain (E. coli NAR) and bromide (Br) as an inert tracer in two soil types. The soils were contaminated at three levels of 0, 0.5 and 1% w/w of total petroleum hydrocarbons (TPHs) using crude oil. Steady-state saturated flow in the soil columns was controlled using a tension infiltrometer. Leaching experiments were conducted through the columns of repacked (un-weathered) and physically-weathered clay loam (CL) and sandy loam (SL) soils. The columns leachate was sampled at specific times for 4 pore volumes. The shape of breakthrough curves for the E. coli NAR and Br depended on soil texture and structure and the TPHs level. Preferential flow in the crude oil-mediated water-repellent soils facilitated the transport of contaminants especially E. coli NAR. Filtration coefficient and relative adsorption index of bacteria were greatest in the repacked CL soils and were lowest in the weathered SL soils. Discontinuity of soil pores and lower flow velocity resulted in greater filtration of E. coli NAR in the repacked CL soil than other treatments. Physical weathering induced the formation of aggregates which reduced soil particle surfaces available for retention of water-repellent oil and contaminants. Movement of both bacteria and Br tracer in the weathered SL soil with 1% TPHs was higher than other treatments. This finding was attributed to low specific surface area, continuity of the pores and water repellency-mediated preferential pathways in the weathered SL soil columns. Our findings implied that shallow groundwater resources could be very sensitive to microbial contamination particularly in the oil-mediated water-repellent soils.