Analytical chemistry of metallic nanoparticles in natural environments

The use of metallic nanoparticles (NPs) has exponentially increased in the past decade due to their unique physical and chemical properties at nano-scales [1]. They are added to a myriad of materials and compositions. The key question is not if NPs will enter environmental compartments but rather when. The fate and the stability of NPs in the environment play important roles in determining their environmental distributions and probably control the risk to human health through exposure. Emissions of nanomaterials (NMs) could be intentional or unintentional but occur in particulate, aggregate or embedded states.Despite environmental transformations and changes in their surrounding environment, metallic NPs (M-NPs) tend to exist as stable colloidal aggregates or dispersions. Characterizing NPs and NMs in environmental samples implies determination of their size, their chemical composition and their bulk concentrations in the matrix. Differential size filtration is the most commonly used method to isolate NPs from aqueous matrices. Micro-filtration, nano-filtration, cross-flow filtration, and ultracentrifugation are usually employed to achieve the highest degree of segregation.Chemical characterization of NPs and NMs has traditionally been done using transmission/scanning electron microscopy (TEM/SEM) followed by energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). However, because of their intrinsic limitations, methods have also been combined and validated [e.g., size exclusion and ion chromatography (SEC and IC) with multi-element detection {inductively-coupled plasma mass spectrometry and optical emission spectroscopy (ICP-MS and ICP-OES)].This review describes the current state and the challenges of isolating, segregating and detecting M-NPs in environmental samples. A simple case study shows a common procedure for the analysis of NPs in complex aqueous matrices.     

Potentials and potentialities of cathodic stripping voltammetry of trace elements in natural waters

Recent advances in voltammetry are discussed. The main advances made are related to the deposition step which now normally utilizes deposition by adsorption rather than by plating. This change suggests that equipment could now be usefully redesigned to provide fast wave-forms such as the high-frequency square-wave modulation as standard. An additional advantage of adsorptive deposition over voltammetry is that the opportunity is provided to utilize catalytic effects to enhance the sensitivity further. Voltammetry is especially suited for the automated monitoring of the concentration and chemical speciation of trace elements in natural waters. It is in this area that is has an advantage over multiple-element analytical techniques.     

Determination of phosphorus in natural waters: A historical review

The aim of this paper is to introduce a virtual special issue that reviews the development of analytical approaches to the determination of phosphorus species in natural waters. The focus is on sampling and sample treatment, analytical methods and quality assurance of the data. The export of phosphorus from anthropogenic activities (from diffuse and point sources) can result in increased primary production and eutrophication, and potentially the seasonal development of toxic algal blooms, which can significantly impact on water quality. Therefore the quantification of phosphorus species in natural waters provides important baseline data for studying aquatic phosphorus biogeochemistry, assessing ecosystem health and monitoring compliance with legislation.     

Evaluation of a cloud point extraction approach for the preconcentration and quantification of trace CuO nanoparticles in environmental waters

The cloud point extraction (CPE) of commercial copper(II) oxide nanoparticles (CuO NPs, mean diameter of 28 nm) in water samples was fully investigated. Factors such as Triton X-114 (TX-114) concentration, pH, incubation temperature and time, were optimized. The effects of CuO NP behavior like agglomeration, dissolution, and surface adsorption of natural organic matter, Cu²⁺, and coating chemicals, on its recovery were studied. The results indicated that all the CPE factors had significant effects on the extraction efficiency. An enrichment factor of ∼89 was obtained under optimum CPE conditions. The hydrodynamic diameter of CuO NPs increased to 4–5 μm upon agglomeration of NP-micelle assemblies, and decreased at pH >10.0 at which the extraction efficiency was also lowered. The solubility and therefore, the loss of NPs were greatly enhanced at pH <8.5 and in the first 60 min of incubation, whereas it declined at elevated incubation temperatures. Our results showed that the dissolved organic carbon (DOC) >5 mg C L⁻¹ and Cu²⁺ >2 times that of CuO NPs, lowered and enhanced the extraction efficiency, respectively. Pre-treatment of samples with 3% w v⁻¹ of hydrogen peroxide and 10 mM of ethylenediaminetetraacetic acid minimized the interferences posed by DOC and Cu²⁺, respectively. The decrease in CPE efficiency was also evident for ligands like poly(ethylene glycol). The TX-114-rich phase could be determined with either inductively coupled plasma mass spectrometry following microwave digestion, or graphite furnace atomic absorption spectrometry. The detection limits for CuO NPs were 0.02 and 0.06 μg L⁻¹ using these techniques, respectively. The optimum sample pre-treatment and CPE conditions were successfully applied to the river and wastewater samples. The relative recoveries of CuO NPs spiked at 5–100 μg L⁻¹ (as Cu) in these samples were in the range of between 59.2 and 108.2%. The approach demonstrates a robust analytical method for detecting trace levels of CuO NPs at their original states and assessing their exposure risks in real aquatic environments.     

Determination of engineered nanoparticles on textiles and in textile wastewaters

Textile materials with engineered nanoparticles (ENPs) have excellent properties as they are antibacterial, antimicrobial, water resistant and protective. The textile industry has recognized the importance and the advantages of ENPs, so they comprise one of the fastest developing branches of processing.The most important sources of ENPs released to the environment from textiles are textile-industry wastewaters and waters from large hospital or hotel laundries. In addition, waste textile materials coated with ENPs present a threat to the environment, if such materials are not properly handled and disposed of after use.Currently, the toxicity and the potential harm of ENPs widely applied on textiles are not thoroughly investigated and/or eliminated. Consequently, there is an urgent need to define the most appropriate analytical methods for monitoring ENPs on textiles.This review presents the most important techniques for monitoring ENPs on textile materials and in textile-wastewater samples, from the perspective of protecting the environment and human health.     

Analytical issues in monitoring drinking-water contamination related to short-term, heavy rainfall events

Heavy rainfall events, increasing in frequency and intensity with climate change, impact on the quality of the water resource used for drinking-water production. Small-scale water suppliers are particularly sensitive because of their management and the related difficulties of adapting treatment to variations. Decision-support systems, based on monitoring and analytical tools, need to be developed to improve crisis-management procedures related to such events. After presenting the issues related to heavy rainfall events, the article summarizes the tools currently used for quality control of drinking water within this framework, the need for developments and other requirements.     

Liquid chromatography with diode array detection and multivariate curve resolution for the selective and sensitive quantification of estrogens in natural waters

Following the green analytical chemistry principles, an efficient strategy involving second-order data provided by liquid chromatography (LC) with diode array detection (DAD) was applied for the simultaneous determination of estriol, 17β-estradiol, 17α-ethinylestradiol and estrone in natural water samples. After a simple pre-concentration step, LC–DAD matrix data were rapidly obtained (in less than 5 min) with a chromatographic system operating isocratically. Applying a second-order calibration algorithm based on multivariate curve resolution with alternating least-squares (MCR-ALS), successful resolution was achieved in the presence of sample constituents that strongly coelute with the analytes. The flexibility of this multivariate model allowed the quantification of the four estrogens in tap, mineral, underground and river water samples. Limits of detection in the range between 3 and 13 ng L⁻¹, and relative prediction errors from 2 to 11% were achieved.