The hydrothermal preparation of o-dianisidine and triazine interlinked porous organic polymer and its successive derivatisation via metal infusion (Ni, Cu) under hydrothermal and calcination conditions (700 °C) to yield pristine (ANIPOP-700) and Ni/Cu decorated porous carbon are described here (Ni-ANIPOP-700 and Cu-ANIPOP-700). To confirm their chemical and morphological properties, the as-prepared materials were methodically analyzed using solid state ¹³C and ¹⁵N NMR, X-ray diffraction, Raman spectroscopy, field emission scanning and high resolution transmission electron microscopic techniques, and x-ray photoelectron spectroscopy. Furthermore, the electrocatalytic activities of these electrocatalysts were thoroughly investigated under standard oxygen evolution (OER) and hydrogen evolution reaction (HER) conditions. The results show that all of the materials demonstrated significant activity in water splitting as well as displayed excellent stability (22 h) in both acidic (HER) and basic conditions (OER). Among the electrocatalysts reported in this study, Ni-ANIPOP-700 exhibited a lower overpotential η₁₀ of 300 mV in basic medium (OER) and 150 mV in acidic medium (HER), as well as a lower Tafel slope of 69 mV/dec (OER) and 181 mV/dec (HER), indicating 30% lower energy requirement for overall water splitting. Gas chromatography was used to examine the electrolyzed products.

Plastic polymers act as passive samplers in air system and concentrate hydrophobic organic contaminants by sorption or specific interactions, which can be transported to other systems such as the marine environment. In this study plastic debris was sampled in the surrounding area of a Mediterranean lagoon in order to determine the concentration of persistent and emerging organic contaminants. More specifically, desorption of 91 regulated and emerging organic contaminants (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, organochlorinated pesticides, current-use pesticides, personal care products, other pesticides and plastic additives) was characterized for the first 24 h from different polymers to seawater and the remaining content of these contaminants was also extracted by ultrasonic extraction with methanol. All samples were analyzed by Stir Bar Sorptive Extraction coupled to GC/MS. A significant fraction of sorbed contaminants in polymers was desorbed in the first 24 h, particularly for triazines and organophosphorus pesticides due to their lower hydrophobicity than other considered analytes. The remaining contaminants contained in plastics can be also transferred to seawater, sediments or biota. Considering 24 h desorbed fraction plus the remaining methanol extracted fraction, the highest transfer levels corresponded to personal care products, plastic additives, current-use pesticides and PAHs. This is the first study to show the relevance of the transport of organic contaminants on plastic debris from littoral areas to the marine environment.

Phosphor imager autoradiography is a technique for rapid, sensitive analysis of the localization of xenobiotics in plant tissues. Use of this technique is relatively new to research in the field of plant science, and the potential for enhancing visualization and understanding of plant uptake and transport of xenobiotics remains largely untapped. Phosphor imager autoradiography is used to investigate the uptake and translocation of the explosives 1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene within Populus deltoides × nigra DN34 (poplar) and Panicum vigratum Alamo (switchgrass). In both plant types, TNT and/or TNT-metabolites remain predominantly in root tissues while RDX and/or RDX-metabolites are readily translocated to leaf tissues. Phosphor imager autoradiography is further investigated for use in semi-quantitative analysis of uptake of TNT by switchgrass. Phosphor imager autoradiography allows for rapid localization and quantification of RDX, TNT, and/or metabolites in plant tissues.

We describe TNT's inhibition of RDX and HMX anaerobic degradation in contaminated soil containing indigenous microbial populations. Biodegradation of RDX or HMX alone was markedly faster than their degradation in a mixture with TNT, implying biodegradation inhibition by the latter. The delay caused by the presence of TNT continued even after its disappearance and was linked to the presence of its intermediate, tetranitroazoxytoluene. PCR-DGGE analysis of cultures derived from the soil indicated a clear reduction in microbial biomass and diversity with increasing TNT concentration. At high-TNT concentrations (30 and 90 mg/L), only a single band, related to Clostridium nitrophenolicum, was observed after 3 days of incubation. We propose that the mechanism of TNT inhibition involves a cytotoxic effect on the RDX- and HMX-degrading microbial population. TNT inhibition in the top active soil can therefore initiate rapid transport of RDX and HMX to the less active subsurface and groundwater. TNT and its metabolites are cytotoxic for RDX and HMX-degrading bacteria in polluted soil.

As part of the Endis-Risks project, the current study describes the occurrence of the chlorotriazine pesticides atrazine, simazine and terbutylazine in water, sediment and suspended matter in the Scheldt estuary (B-Nl) from 2002 to 2005 (3 samplings a year, 8 sampling points). Atrazine was found at the highest concentrations, varying from 10 to 736 ng/l in water and from 5 up to 10 ng/g in suspended matter. Simazine and terbutylazine were detected at lower concentrations. Traces of the targeted pesticides were also detected in sediments, but these were below the limit of quantification. As part of an ecotoxicological assessment, we studied the potential effect of atrazine on molting of Neomysis integer (Crustacea:Mysidacea), a resident invertebrate of the Scheldt Estuary and a proposed test organism for the evaluation of endocrine disruption. Following chronic exposure (3 weeks), atrazine did not significantly affect mysid molting at environmentally relevant concentrations (up to 1 μg/l). The water of the Scheldt estuary and its associated suspended solids are contaminated with chlorotriazines at concentrations that do not affect mysid molting.

Zerovalent iron (Fe0, ZVI) has drawn great interest as an inexpensive and effective material to promote the degradation of environmental contaminants. A focus of ZVI research is to increase degradation kinetics and overcome passivation for long-term remediation. Halide ions promote corrosion, which can increase and sustain ZVI reactivity. Adding chloride or bromide salts with Fe0 (1% w/v) greatly enhanced TNT, RDX, and HMX degradation rates in aqueous solution. Adding Cl or Br salts after 24 h also restored ZVI reactivity, resulting in complete degradation within 8 h. These observations may be attributed to removal of the passivating oxide layer and pitting corrosion of the iron. While the relative increase in degradation rate by Cl- and Br- was similar, TNT degraded faster than RDX and HMX. HMX was most difficult to remove using ZVI alone but ZVI remained effective after five HMX reseeding cycles when Br- was present in solution. The addition of halide ions promotes the degradation of high explosives by zerovalent iron.

Triafamone, a sulfamide herbicide, has been extensively utilized for weed control in rice paddies in Asia. However, its fate and transformation in the environment have not been established. Through a rice paddy microcosm-based simulation trial combined with multiple spectroscopic analyses, we isolated and identified three novel metabolites of triafamone, including hydroxyl triafamone (HTA), hydroxyl triafamone glycoside (HTAG), and oxazolidinedione triafamone (OTA). When triafamone was applied to rice paddies at a concentration of 34.2 g active ingredient/ha, this was predominantly distributed in the paddy soil and water, and then rapidly dissipated in accordance with the first-order rate model, with half-lives of 4.3–11.0 days. As the main transformation pathway, triafamone was assimilated by the rice plants and was detoxified into HTAG, whereas the rest was reduced into HTA with subsequent formation of OTA. At the senescence stage, brown rice had incurred triafamone at a concentration of 0.0016 mg/kg, but the hazard quotient was <1, suggesting that long-term consumption of the triafamone-containing brown rice is relatively safe. The findings of the present study indicate that triafamone is actively metabolized in the agricultural environment, and elucidation of the link between environmental exposure to these triazine or oxazolidinedione moieties that contain metabolites and their potential impacts is warranted.

The exposures of pharmaceutical antibiotics in water solution caused potential risks for ecological environment and human health. In the present study, porous covalent triazine frameworks (CTFs) were synthesized and the adsorption behavior of sulfamethoxazole (SMX) and tylosin (TL) was investigated. The CTFs were characterized by X-ray diffraction, transform infrared and N2 adsorption/desorption. Sulfamethoxazole displayed much stronger adsorption than tylosin on microporous CTF-1 adsorbent due to the pore-filling effect. While the adsorption of bulky tylosin on microporous CTF-1 was suppressed because of the size exclusion effect. Additionally, the porous CTFDCBP showed stronger adsorption affinity and faster adsorption kinetics than other porous adsorbents, which was attributed to wide pore size distribution and open pore structure. Findings in this study highlight the potential of using porous CTFs as a potential adsorbent to eliminate antibiotics from water, especially for selective adsorption of bulky molecular pollutant.

2,4,6-Trinitrotoluene (TNT) metabolism was compared across salinity transects in Kahana Bay, a small tropical estuary on Oahu, HI. In surface water, TNT incorporation rates (range: 3–121 μg C L−1 d−1) were often 1–2 orders of magnitude higher than mineralization rates suggesting that it may serve as organic nitrogen for coastal microbial assemblages. These rates were often an order of magnitude more rapid than those for RDX and two orders more than HMX. During average or high stream flow, TNT incorporation was most rapid at the riverine end member and generally decreased with increasing salinity. This pattern was not seen during low flow periods. Although TNT metabolism was not correlated with heterotrophic growth rate, it may be related to metabolism of other aromatic compounds. With most TNT ring-carbon incorporation efficiencies at greater than 97%, production of new biomass appears to be a more significant product of microbial TNT metabolism than mineralization.