Removal of benzotriazole derivatives by biochar: Potential environmental applications.

Benzotriazole and its derivatives (BTAs) are commonly present in wastewater due to their extensive use in industrial processes, yet their removal is still unexplored. Here, we test the removal of these pollutants using two functionalised biochars, synthesised from wild plum (WpOH) and apricot (AsPhA) kernels. The aim of this work was to optimise the adsorption process against various BTAs (i.e., benzotriazole (BTZ), 4-hydroxy-1H-benzotriazole (OHBZ), 4-methyl-1H-benzotriazole (4 MBZ), 5-methyl-1H-benzotriazole (5 MBZ), 5-chloro-1H-benzotriazole (ClBZ), 5,6-dimethyl-1H-benzotriazole (DMBZ)), and determine the adsorption mechanisms at play, using real wastewater matrices. Batch studies showed that the optimal adsorption pH ranged between 4 and 6 for WpOH and AsPhA, respectively, and equilibrium was reached after 240 min. The kinetic models that best described the adsorption process were in the following order: Elovich model > pseudo-second order model > pseudo-first order model. The equilibrium data showed the highest correlation with the Freundlich isotherm, indicating multilayer adsorption. The maximum adsorption capacity obtained in mixtures was 379 mg/g on WpOH and 526 mg/g on AsPhA. The mechanistic work revealed that the BTAs became bound to the biochar primarily through H-bonding, n-π and π-π EDA interactions. In wastewater, obtained before and after conventional treatment, the concentration of OHBZ and BTZ was reduced by >40%, while the concentration of the other compounds studied fell below the detection limit (∼2.0-90 ng/L). Finally, using a Vibrio fischeri assay, we showed that adsorption onto AsPhA significantly reduced the relative toxicity of both raw and treated wastewater.

Determination of Cellulose Degree of Polymerization in Historical Papers with High Lignin Content.

Determination of cellulose degree of polymerization (DP) is one of the most commonly used methods in paper degradation studies, performed either by a standardized method using viscometry (as average degree of polymerization (DPv)) or size-exclusion chromatography (SEC) (as weight average molecular mass (Mw)). Due to the insolubility of papers with high lignin content in cupriethylenediamine (CED), such as groundwood papers, viscometric determination is not possible; therefore, pretreatment is required to allow subsequent dissolution of the papers. In this study, the pretreatment of historical papers containing groundwood with sodium chlorite in acetic acid was investigated, which enables dissolution of the paper samples in CED and determination of the cellulose average degree of polymerization by viscometry (DPv). Kappa number was determined to estimate the lignin content in the papers. The suitability of SEC UV-VIS analysis for determination of Mw in papers with high lignin content had been verified before it was used as a comparative method for viscometry. Using SEC, changes in the weight average molecular mass (Mw) of cellulose tricarbanilate (CTC) derivative during delignification were evaluated. The results indicate that no significant depolymerization occurred in the selected samples under the studied delignification conditions, which was additionally confirmed with determination of monosaccharides by ion chromatography. The results of the Mw determinations by SEC and DPv by viscometry are in good correlation, justifying the use of viscometry after chlorite/acetic acid pretreatment to determine the cellulose average degree of polymerization in historical papers with high lignin content.

Non-Destructive Detection of Pentachlorophenol Residues in Historical Wooden Objects.

Wood is a natural polymeric material that is an important constituent of many heritage collections. Because of its susceptibility to biodegradation, it is often chemically treated with substances that can be harmful to human health. One of the most widely used wood preservatives was pentachlorophenol (PCP), which is still present in museum objects today, although its use has been restricted for about forty years. The development of non-destructive methods for its determination, suitable for the analysis of valuable objects, is therefore of great importance. In this work, two non-destructive solid-phase microextraction (SPME) methods were developed and optimized, using either headspace or contact mode. They were compared with a destructive solvent extraction method and found to be suitable for quantification in the range of 7.5 to 75 mg PCP/kg wood at room temperature. The developed semi-quantitative methods were applied in the wooden furniture depot of National Museum of Slovenia. PCP was detected inside two furniture objects using headspace mode. The pesticide lindane was also detected in one object. The indoor air of the depot with furniture was also sampled with HS SPME, and traces of PCP were found. According to the results, SPME methods are suitable for the detection of PCP residues in museum objects and in the environment.

Development of a Dispersive Liquid-Liquid Microextraction Followed by LC-MS/MS for Determination of Benzotriazoles in Environmental Waters.

Emerging environmental pollutants are becoming a global concern, since the acceptable concentrations are currently not set by legislation in EU or elsewhere. Benzotriazoles are an important group of emerging pollutants found in low µg/L concentrations, entering the environment through wastewater treatment facilities due to their insufficient removal, and through industrial and other use. Two new dispersive liquid-liquid microextraction (DLLME) methods were developed for the extraction of hydrophilic and hydrophobic benzotriazoles from environmental waters. Liquid chromatographic method coupled to tandem mass spectrometric detection (LC-MS/MS) was developed and validated for surface water. Validation parameters were satisfactory and the overall DLLME-LC-MS/MS method was found to be applicable to analysis of the chosen analytes in environmental waters. It was used to determine benzotriazoles in surface water and wastewater from a municipal wastewater treatment plant. In surface waters, concentration was below the limit of detection, while concentrations determined in wastewater were estimated between 2.7 and 12.0 µg/L.

Solid-Phase Extraction of Polar Benzotriazoles as Environmental Pollutants: A Review.

Polar benzotriazoles are corrosion inhibitors with widespread use; they are environmentally characterized as emerging pollutants in the water system, where they are present in low concentrations. Various extraction methods have been used for their separation from various matrices, ranging from classical liquid⁻liquid extractions to various microextraction techniques, but the most frequently applied extraction technique remains the solid-phase extraction (SPE), which is the focus of this review. We present an overview of the methods, developed in the last decade, applied for the determination of benzotriazoles in aqueous and solid environmental samples. Several other matrices, such as human urine and plant material, are also considered in the text. The methods are reviewed according to the determined compounds, sample matrices, cartridges and eluents used, extraction recoveries and the achieved limits of quantification. A critical evaluation of the advantages and drawbacks of the published methods is given.