2,4,6-trinitrotoluene (TNT) is a highly toxic explosive that contaminates soil and water and may interfere with the degradation of co-occurring compounds, such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). We proposed that TNT may influence RDX-degrading bacteria via either general toxicity or a specific effect on the |RDX degradation mechanisms. Thus, we examined the impact of TNT on RDX degradation by Rhodococcus strains YH1, T7, and YY1, which were isolated from an explosives-polluted environment. Although partly degraded, TNT did not support the growth of any of the strains when used as either sole carbon or sole nitrogen sources, or as carbon and nitrogen sources. The incubation of a mixture of TNT (25 mg/l) and RDX (20 mg/l) completely inhibited RDX degradation. The effect of TNT on the cytochrome P450, catalyzing RDX degradation, was tested in a resting cell experiment, proving that TNT inhibits XplA protein activity. A dose-response experiment showed that the IC50/trans values for YH1, T7, and YY1 were 7.272, 5.098, and 9.140 (mg/l of TNT), respectively, illustrating variable sensitivity to TNT among the strains. The expression of xplA was also strongly suppressed by TNT. Cells that were pre-grown with RDX (allowing xplA expression) and incubated with ammonium chloride, glucose, and TNT, completely transformed into their amino dinitrotoluene isomers and formed azoxy toluene isomers. The presence of oxygen-insensitive nitroreductase that enable reduction of the nitro group in the presence of O2 in the genomes of these strains suggests that they are responsible for TNT transformation in the cultures. The experimental results concluded that TNT has an adverse effect on RDX degradation by the examined strains. It inhibits RDX degradation due to the direct impact on cytochrome P450, xplA, or its expression. The tested strains can transform TNT independently of RDX. Thus, degradation of both compounds is possible if TNT concentrations are below their IC50 values.

Fate of nonylphenol (NP) in soils and the effects of nitrogen fertilizers are unclear. Using 14C-tracer, we studied the aerobic and anaerobic degradation of 4-NP111 in a paddy red soil amended without and with ammonium chloride. Under oxic conditions, 4-NP111 had a half-life of 16.1 ± 1.6 days and minor mineralization (3.84 ± 0.02%), forming no extractable metabolite but abundant bound residues (60.9 ± 1.7%, mostly bound to humin) after 49 days of incubation. The ammonium amendment (8 mmol/kg soil) significantly inhibited the degradation (half-life of 68.0 ± 7.7 days), mineralization (2.0 ± 1.1%), and bound-residue formation (23.7 ± 0.2%). Under anoxic conditions, 4-NP111 did not degrade during 49 days of incubation and the ammonium amendment (40 mmol/kg soil) did not affect its persistence. Our results demonstrate that bound-residue formation was a major mechanism for NP dissipation in the red soil under oxic conditions and that chemical nitrogen fertilizer at average field application rate may already considerably increase NP recalcitrance in agricultural soils.

This study investigated the physiological response of the epiphytic lichen Evernia prunastri to ecologically relevant concentrations of nitrogen compounds. Lichen samples were sprayed for 4 weeks either with water or 50, 150 and 500 μM NH₄Cl. The integrity of cell membranes and chlorophyll a fluorescence emission (FV/FM and PIABS) were analyzed. No membrane damage occurred after the exposure period. FV/FM, a classical fluorescence indicator, decreased during the second week of treatment with 500 μM NH₄Cl and the third week with 50 and 150 μM NH₄Cl. PIABS, an overall index of the photosynthetic performance, was more sensitive and decreased already during the first week with 500 μM NH₄Cl and the second week with 150 μM NH₄Cl. Since E. prunastri has been exposed to ammonium loads corresponding to real environmental conditions, these findings open the way to an effective use of this species as early indicators of environmental nitrogen excess.

Simultaneous quantification of short-, medium-, and long-chain chlorinated paraffins (CPs) in environmental matrices is challenging and has received much attention from environmental chemists. In this study, ammonium-chloride-enhanced liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS) was developed for the first time to quantify CPs in sediments and aqueous samples. Three ionization sources, including atmospheric pressure chemical ionization (APCI), electrospray ionization (ESI), and thermal-assisted-ESI, were employed to examine the performance of ammonium chloride as the chloride ion supply reagent in comparison with traditional chloride ion supply reagent, dichloromethane. Ammonium chloride can be easily used with reversed-phase liquid chromatography (LC), whereas dichloromethane is not compatible with aqueous LC mobile phase. Furthermore, other anion-supply reagents, such as ammonium formate, ammonium acetate, and ammonium bromide, were also tested. It was concluded that the adducts of the CPs with the anions were reversible and could partially dissociate into deprotonated CP ions. The yield of deprotonated CP ions was associated with the gas-phase basicity of the deprotonated CP ions and the corresponding anions. Furthermore, collision-induced dissociation curves were drawn to quantify the stability of anionic CP adducts. The ammonium-chloride-enhanced LC-HRMS was further employed for identifying CPs in sediment samples and coupled with an online SPE method for detecting CPs in aqueous samples. This study may significantly contribute to the qualification and quantification of CPs in environmental matrices.

Benzylalkyldimethylethyl ammonium compounds are pervasive in natural environments and toxic at high concentrations. The changes in functional genes and microbial diversity in eutrophic lake samples exposed to benzyldimethyldodecyl ammonium chloride (BAC) were assessed. BAC exerted negative effects on bacteria abundance, particularly at concentrations of 100 μg L−1 and higher. A significant increase in the number of the quaternary ammonium compound-resistant gene qacA/B was recorded within the 10 μg L−1 treatment after the first day of exposure. Not all antibiotic resistance genes increased in abundance as the concentrations of BAC increased; rather, gene abundances were dependent on the gene type, concentrations of BAC, and contact time. The nitrogen fixation-related gene nifH and ammonia monooxygenase gene amoA were inhibited by high concentrations of BAC after the first day, whereas an increase of the nitrite reductase gene nirK was stimulated by exposure. Microbial communities within higher treatment levels (1000 and 10 000 μg L−1) exhibited significantly different community composition compared to other treatment levels and the control. Selective enrichment of Rheinheimera, Pseudomonas, and Vogesella were found in the higher treatment levels, suggesting that these bacteria have some resistance or degradation capacity to BAC. Genes related with RNA processing and modification, transcription, lipid transport and metabolism, amino acid transport and metabolism, and cell motility of microbial community function were involved in the process exposed to the BAC stress.

Extracellular Polymeric Substances (EPS) influenced Poly Cyclic Aromatic Hydrocarbons (PAHs) degrading Klebsiella pneumoniae was isolated from the marine environment. To increase the EPS production by Klebsiella pneumoniae, several physicochemical parameters were tweaked such as different carbon sources (arabinose, glucose, glycerol, lactose, lactic acid, mannitol, sodium acetate, starch, and sucrose at 20 g/L), nitrogen sources (ammonium chloride, ammonium sulphate, glycine, potassium nitrate, protease peptone and urea at 2 g/L), different pH, carbon/nitrogen ratio, temperature, and salt concentration were examined. Maximum EPS growth and biodegradation of Anthracene (74.31%), Acenaphthene (67.28%), Fluorene (62.48%), Naphthalene (57.84%), and mixed PAHs (55.85%) were obtained using optimized conditions such as glucose (10 g/L) as carbon source, potassium nitrate (2 g/L) as the nitrogen source at pH 8, growth temperature of 37 °C, 3% NaCl concentration and 72 h incubation period. The Klebsiella pneumoniae biofilm architecture was studied by confocal laser scanning microscopy (CLSM) and scanning electron microscope (SEM). The present study demonstrates the EPS influenced PAHs degradation of Klebsiella pneumoniae.

Phytoextraction using Celosia argentea Linn. can potentially decontaminate Cd-contaminated soils. However, most earlier studies have been conducted at laboratory scale and for a relatively short remediation period. To evaluate the phytoextraction efficiency of C. argentea combined with different soil amendments (ammonium chloride, Bacillus megaterium, and citric acid), an 18-month field experiment was carried out in a farmland soil contaminated with 3.68 mg kg⁻¹ Cd by mine tailings in southern China. Soil Cd concentrations were decreased by 6.34 ± 0.73% after the three harvestings (with no amendments), which was 2.27 times that of the no-planting control (p < 0.05). Application of ammonium chloride, B. megaterium, and citric acid increased the overall Cd reduction rate in soil by 40.5%, 46.1%, and 105%, respectively. The application of citric acid decreased total Cd in soil by up to 16.9% in the rhizosphere soil and 13.0% in the bulk soil. The highest annual shoot biomass yield and Cd extraction amount reached 8.79 t ha⁻¹ and 273 g ha⁻¹. Acid-soluble Cd fraction in the rhizosphere was significantly lower compared to that in the bulk soil (p < 0.05), which indicates that mobile Cd in the rhizosphere was taken up by the roots vastly. C. argentea phytoextraction also improved soil metabolic functions by increasing the activities of soil enzymes (urease, invertase, phosphatase, and catalase). These findings demonstrate that Cd phytoextraction using C. argentea with the application of soil amendments can greatly improve the quality of Cd-contaminated soils.

Studies were conducted to assess the biodegradability and toxicity of the cationic surfactant dodecyl trimethyl ammonium chloride (DTMAC) in sea water samples collected from the Gulf of Cadiz (Spain). Ultimate biodegradation was studied following the guideline proposed by the United States Environmental Protection Agency (USEPA). Growth inhibition tests on five marine microalgae species and mortality tests on a marine crustacean (Artemia franciscana) were carried out. Biodegradation process was modelled according to a logistic kinetic model. Lag time and half-life were 15.17 and 26.95 days, respectively. Depending on the microalgae, 96-h EC50 values ranged from 0.69 to 6.34 mg L⁻¹ DTMAC, respectively. 48-h and 72-h LC50 to A. franciscana were 46.74 and 34.19 mg L⁻¹ DTMAC, respectively. The results indicate that DTMAC can be mineralised in sea water. Marine crustacean was more resistant than the microalgae. Surfactant tolerance on microalgae followed this order: T. chuii > N. gaditana > C. gracilis ≈ I. galbana ≈ D. salina, being the Green microalgae T. chuii the most tolerant.

A new adsorbent poly-3-hydroxybutyrate-2-(dodecylthiocarbonothioylthio)-2-methylpropionate triester (PH-DTT-MPT) was first time loaded in a micropipette tip for speciation of chromium in different water samples. Total chromium (Cr), trivalent chromium (Crᴵᴵᴵ), and hexavalent chromium (Crⱽᴵ) in different natural water samples were determined by electrothermal atomic absorption spectrometry. Known concentration of Crᴵᴵᴵ and Crⱽᴵ was passed through a biodegradable polymer for investigation of the behavior of the newly used adsorbent. The newly used copolymer absorbed the Crᴵᴵᴵ on surface of the PH-DTT-MPT at pH 7.0, while Crⱽᴵ was not adsorbed in desired pH value. After passing the real and standard solutions through the micropipette, then 2.0 mol L⁻¹ HCl was used for elution of Crᴵᴵᴵ from the biodegradable polymer. Total Cr was calculated after reducing Crⱽᴵ into Crᴵᴵᴵ by specific concentration of hydroxy ammonium chloride (HONH₂·HCl). The concentration of Crⱽᴵ in different natural water samples was estimated after back calculation of Crᴵᴵᴵ from total chromium. Effect of analytical parameters like adsorbent, pH, eluent, sample volume, flow rates, and interfering ions was also studied. The LOD, LOQ, RSD, and EF of the developed method were calculated as 6.1 ng L⁻¹, 20 ng L⁻¹, 1.17%, and 90, respectively. Validation of developed method was checked by certified reference materials and spiking addition method. The developed method was successfully applied for determination of total Cr, Crᴵᴵᴵ, and Crⱽᴵ in various natural water ecosystems.