Toxicity data of substances to higher plants is needed for the purpose of risk assessment, site evaluation, phytoremediation, and plant protection. However, the results from the most common phytotoxicity tests, like the OECD algae and Lemna test, are not necessarily valid for higher terrestrial plants. The willow tree toxicity test uses inhibition of transpiration (aside of growth and water use efficiency) of willow cuttings grown in spiked solutions or soils as end point to quantify toxicity. This overview presents results from 60 studies including 24 new unpublished experiments for 56 different chemicals or substrates. Highest toxicity (EC₅₀ < 1 mg/L) was observed from exposure to heavy metals like copper and cadmium. Also, organotins and free cyanide showed very high toxicity. The toxic effect of chlorophenols on willows was comparable to that on duck weed (Lemna) and green algae, while volatile compounds like chlorinated solvents or benzene, toluene, ethylbenzene, and xylene had less effect on trees than on these aquatic plants, due to volatilization from leaves and test media. In particular low (g/L range) toxicity was observed for tested nanomaterials. Effects of pharmaceuticals (typically weak acids or bases) depended strongly of the solution pH. Like for algae, baseline toxicity was observed for willows, which is related to the water solubility of the compounds, with absolute chemical activity ranging from 0.01 to 0.1, but with several exceptions. We conclude that the willow tree toxicity test is a robust method for relating uptake, accumulation, and metabolism of substances to the toxicity to trees.

Two indigenous bacterial strains, Bacillus megaterium ETLB-1 (accession no. KC767548) and Pseudomonas plecoglossicida ETLB-3 (accession no. KC767547), isolated from soil contaminated with paper mill effluent, were co-immobilized on corncob cubes to investigate their biodegradation potential against black liquor (BL). Results exhibit conspicuous reduction in color and lignin of BL upto 913.46 Co-Pt and 531.45 mg l⁻¹, respectively. Reduction in chlorophenols up to 12 mg l⁻¹was recorded with highest release of chloride ions, i.e., 1290 mg l⁻¹. Maximum enzyme activity for lignin peroxidase (LiP), manganese peroxidase (MnP), and laccase (LAC) was recorded as 5.06, 8.13, and 8.23 U ml⁻¹, respectively, during the treatment. Scanning electron microscopy (SEM) revealed successful immobilization of bacterial strains in porous structures of biomaterial. Gas chromatography/mass spectroscopy (GC/MS) showed formation of certain low molecular weight metabolites such as 4-hydroxy-benzoic acid, 3-hydroxy-4-methoxybenzaldehyde, ferulic acid, and t-cinnamic acid and removal of majority of the compounds (such as teratogenic phthalate derivatives) during the period of treatment. Results demonstrated that the indigenous bacterial consortium possesses excellent decolorization and lignin degradation capability which enables its commercial utilization in effluents treatment system.

2,4-Dichlorophenol (2,4-DCP) is widely distributed in wastewaters discharged from several industries, and it is considered as a priority pollutant due to its high toxicity. In this study, the use of different peroxidase extracts for 2,4-DCP removal from aqueous solutions was investigated. Tobacco hairy roots (HRs), wild-type (WT), and double-transgenic (DT) for tomato basic peroxidases (TPX1 and TPX2) were used to obtain different peroxidase extracts: total peroxidases (TPx), soluble peroxidases (SPx), and peroxidases ionically bound to the cell wall (IBPx). All extracts derived from DT HRs exhibited higher peroxidase activity than those obtained from WT HRs. TPx and IBPx DT extracts showed the highest catalytic efficiency values. The optimal conditions for 2,4-DCP oxidation were pH 6.5, H₂O₂0.5 mM, and 200 U mL⁻¹of enzyme, for all extracts analyzed. Although both TPx extracts were able to oxidize different 2,4-DCP concentrations, the removal efficiency was higher for TPx DT. Polyethylene glycol addition slightly improved 2,4-DCP removal efficiency, and it showed some protective effect on TPx WT after 2,4-DCP oxidation. In addition, using Lactuca sativa test, a reduction of the toxicity of post removal solutions was observed, for both TPx extracts. The results demonstrate that TPx extracts from both tobacco HRs appear to be promising candidate for future applications in removing 2,4-DCP from wastewaters. This is particularly true considering that these peroxidase sources are associated with low costs and are readily available. However, TPx DT has increased peroxidase activity, catalytic efficiency, and higher removal efficiency than TPx WT, probably due to the expression of TPX1 and TPX2 isoenzymes.

Background, aim and scope Photochemical processes can decontaminate the aqueous environment from xenobiotics, but they also produce secondary pollutants. This paper presents field and laboratory evidence of the transformation of 4-chlorophenol (4CP) into 2-nitro-4-chlorophenol (2N4CP). Materials and methods Field monitoring of 4CP and 2N4CP was carried out by solid phase extraction coupled with liquid chromatography-multiple reaction monitoring mass spectrometry. Laboratory irradiation experiments were carried out under a UV-Vis lamp, and the time evolution of the compounds of interest was followed by liquid chromatography. Purpose The purpose of this study was elucidating the pathways leading to 2N4CP from 4CP in paddy field water. Results and discussion The field monitoring results suggest that 4CP can be transformed into 2N4CP in the paddy field water of the Rhône delta (Southern France). The laboratory study indicates that the transformation can take place via photonitration by •NO₂. The nitration process is inhibited by bicarbonate, possibly due to basification that favours the occurrence of the 4-chlorophenolate. The latter could consume •NO₂ without being nitrated. Photonitration in the presence of bicarbonate could account for the observed transformation in the field. Conclusions Photonitration of 4CP to 2N4CP by •NO₂ could account for the observed interconversion of the two compounds in paddy fields. The results are of concern because 2N4CP is biorecalcitrant and toxic. Recommendations and perspectives Bicarbonate can modulate the photonitration of 4CP into 2N4CP, which can be very significant in bicarbonate-poor waters.

The main organic pollutants worldwide are pesticides, persistent chemicals that are of concern owing to their prevalence in various ecosystems. In nature, pesticide remainders are subjected to the chemical, physical, and biochemical degradation process, but because of its elevated stability and some cases water solubility, the pesticide residues persist in the ecosystem. The removal of pesticides has been performed through several techniques classified under biological, chemical, physical, and physicochemical process of remediation from different types of matrices, such as water and soil. This review provides a description of older and newer techniques and materials developed to remove specific pesticides according to previous classification, which range from bioremediation with microorganisms, clay, activated carbon, and polymer materials to chemical treatment based on oxidation processes. Some types of pesticides that have been removed successfully to large and small scale include, organophosphorus, carbamates, organochlorines, chlorophenols, and synthetic pyrethroids, among others. The most important characteristics, advantages, and disadvantages of techniques and materials for removing pesticides are described in this work.

In 2009, hexachlorocyclohexane (HCH) isomers (α-HCH, β-HCH, and γ-HCH [lindane]) were listed as persistent organic pollutants (POP) in the Stockholm Convention. Accordingly, the legacy of HCH/lindane production with the associated large HCH waste deposits has become recognized as an issue of global concern and is addressed in the implementation of the Convention. The current paper gives an overview of the major contaminated sites from lindane production of the INQUINOSA Company. This company operated from 1975 to 1988 in the city of Sabiñánigo, Spain. HCH production resulted in the production of approximately 115,000 tonnes of waste isomers which were mainly dumped in two unlined landfills. These two landfill sites, together with the former production site, are recognized sources of environmental pollution. Assessment and remediation activities at these sites are described. A dense nonaqueous phase liquid (DNAPL) contaminated inter alia with HCH isomers, benzene, chlorobenzenes, and chlorophenols as the main contaminants and an associated contaminated groundwater plume have been discovered at both landfill/dumpsites and at the former production site. The approximately 4,000 t of DNAPLs constitute a serious risk for the environment due to the proximity of the Gállego River. Since 2004, more than 20 tonnes of this DNAPL has been extracted using “pump and treat” techniques. The Aragon Regional Government and the Spanish Environmental Ministry are taking action, focusing on the treatment of DNAPL and on the transfer of the large quantities of solid POP wastes to a new landfill. A range of laboratory tests has been performed in order to plan the aquifer remediation.

In this study, a novel inexpensive biosorbent of pine cone powder was used for the treatment of wastewater contaminated with phenol and chlorophenols (CPhs). The biosorbent was thoroughly characterized by using CHN and BET measurements, as well as FTIR, SEM, and XRD analyses. Kinetic and equilibrium biosorption experiments showed that the uptake was more than 80% within the first 30 min of contact time at pH 5.0. The biosorption of 4-CPh onto pine cone powder was higher than those of phenol and 2-CPh. The kinetic data were consistent with the pseudo-first-order kinetic model, and the Langmuir isotherm model best represented the equilibrium data. The maximum biosorption capacities of phenol, 2-CPh, and 4-CPh were 164.51, 189.44, and 220.12 mg/g, respectively, at 30 ± 1 °C. Therefore, the pine cone powder is an effective low-cost adsorbent for the removal of phenol and CPhs from the contaminated water.

The concentrations, homologue, and congener profiles, as well as the gas/particle distribution of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), chlorobenzenes (CBzs), chlorophenols (CPhs), and polyaromatic hydrocarbons (PAHs) from stack gas of two different municipal solid waste incinerators in China, were characterized. The incinerators were a stoker furnace incinerator equipped with the advanced air pollution control device (APCD) and a common circulating fluidized bed (CFB) furnace. The concentration of PCDD/Fs in the stack gas of the stoker incinerator ranged 0.011–0.109 ng international toxic equivalent factor (I-TEQ)/Nm³ and was below the current limit for PCDD/F emissions from the municipal solid waste incinerators (MSWIs) in China (0.1 ng I-TEQ/Nm³) in most of the cases. Moreover, the concentration of PCDD/Fs in the stack gas of the stoker incinerator was significantly lower than that of the CFB incinerator (0.734 to 24.6 ng I-TEQ/Nm³). In both incinerators, the majority of the total PCDD/F emissions (above 90%) ended up in the gas phase. 2,3,4,7,8-PeCDF, which occupied 24.3–43.6 and 32.5–75.6% of I-TEQ contribution in MSWIs A and B, respectively, was the most abundant congener. However, different types of incinerators and APCDs induced different congener and homologue distributions. The total concentration of CBzs from the stoker incinerator (0.05–3.2 μg/Nm³) was also much lower than that formed from the CFB incinerator (10.9–75.2 μg/Nm³). The phase distribution of CBzs followed the same pattern as with the PCDD/Fs. Moreover, the emission level of CBz was 100–1000 times higher than that of the PCDD/Fs, which determines the applicability of CBzs as indicators of PCDD/F emissions. High correlations between the emission concentrations of PCDD/Fs, TeCBz, and PCBz in specific ranges were revealed. Furthermore, high concentrations of CPhs (0.6–141.0 μg/Nm³) and PAHs (148.6–4986.5 μg/Nm³) were detected in the stack gases of MSWI B. In some cases, the concentrations were as high as the concentrations in the fumes exiting the boiler of one foreign stoker without flue gas purification indicating the abundance of CPh and PAH emissions in the stack gas of waste incinerators.

The production and use of chlorophenolic compounds in industry has led to the introduction of many xenobiotics, among them chlorophenols (CPs), into the environment. Five CPs are listed in the priority pollutant list of the U.S. EPA, with pentachlorophenol (PCP) even being proposed for listing under the Stockholm Convention as a persistent organic pollutant (POP). A green procedure for degrading such pollutants is greatly needed. The use of ferrate could be such a process. This paper studies the degradation of CPs (with an emphasis on PCP) in the presence of ferrate both in a spiked demineralized water system as well as in real contaminated groundwater. Results proved that ferrate was able to completely remove PCP from both water systems. Investigation of the effect of ferrate purity showed that even less pure and thus much cheaper ferrate was applicable. However, with decreasing ferrate purity, the degradability of CPs may be lower.

A simple online headspace solid-phase microextraction (HS-SPME) coupled with the gas chromatography-mass spectrometry (GC-MS) method was developed for simultaneous determination of trace amounts of nine estrogenic odorant alkylphenols and chlorophenols and their derivatives in water samples. The extraction conditions of HS-SPME were optimized including fiber selection, extraction temperature, extraction time, and salt concentration. Results showed that divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was the most appropriate one among the three selected commercial fibers, and the optimal extraction temperature, time, and salt concentration were 70 °C, 30 min, and 0.25 g/mL, respectively. The developed method was validated and showed good linearity (R ² > 0.989), low limit of detection (LOD, 0.002–0.5 μg/L), and excellent recoveries (76–126 %) with low relative standard deviation (RSD, 0.7–12.9 %). The developed method was finally applied to two surface water samples and some of these target compounds were detected. All these detected compounds were below their odor thresholds, except for 2,4,6-TCAS and 2,4,6-TBAS wherein their concentrations were near their odor thresholds. However, in the two surface water samples, these detected compounds contributed to a certain amount of estrogenicity, which seemed to suggest that more attention should be paid to the issue of estrogenicity rather than to the odor problem.