Optical Monitoring of Microplastics Filtrated from Wastewater Sludge and Suspended in Ethanol.

The abundance of microplastics (MPs) in the atmosphere, on land, and especially in water bodies is well acknowledged. In this study, we establish an optical method based on three different techniques, namely, specular reflection to probe the medium, transmission spectroscopy measurements for the detection and identification, and a speckle pattern for monitoring the sedimentation of MPs filtrated from wastewater sludge and suspended in ethanol. We used first Raman measurements to estimate the presence and types of different MPs in wastewater sludge samples. We also used microscopy to identify the shapes of the main MPs. This allowed us to create a teaching set of samples to be characterized with our optical method. With the developed method, we clearly show that MPs from common plastics, such as polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS), and polyethylene (PE), are present in wastewater sludge and can be identified. Additionally, the results also indicate that the density of the plastics, which influences the sedimentation, is an essential parameter to consider in optical detection of microplastics in complex natural environments. All of the methods are in good agreement, thus validating the optics-based solution.

Towards the Development of Portable and In Situ Optical Devices for Detection of Micro and Nanoplastics in Water: A Review on the Current Status.

The prevalent nature of micro and nanoplastics (MP/NPs) on environmental pollution and health-related issues has led to the development of various methods, usually based on Fourier-transform infrared (FTIR) and Raman spectroscopies, for their detection. Unfortunately, most of the developed techniques are laboratory-based with little focus on in situ detection of MPs. In this review, we aim to give an up-to-date report on the different optical measurement methods that have been exploited in the screening of MPs isolated from their natural environments, such as water. The progress and the potential of portable optical sensors for field studies of MPs are described, including remote sensing methods. We also propose other optical methods to be considered for the development of potential in situ integrated optical devices for continuous detection of MPs and NPs. Integrated optical solutions are especially necessary for the development of robust portable and in situ optical sensors for the quantitative detection and classification of water-based MPs.

Simultaneous investigation of the liquid transport and swelling performance during tablet disintegration.

Fast disintegrating tablets have commonly been used for fast oral drug delivery to patients with swallowing difficulties. The different characteristics of the pore structure of such formulations influence the liquid transport through the tablet and hence affect the disintegration time and the release of the drug in the body. In this work, terahertz time-domain spectroscopy and terahertz pulsed imaging were used as promising analytical techniques to quantitatively analyse the impact of the structural properties on the liquid uptake and swelling rates upon contact with the dissolution medium. Both the impact of porosity and formulation were investigated for theophylline and paracetamol based tablets. The drug substances were either formulated with functionalised calcium carbonate (FCC) with porosities of 45% and 60% or with microcrystalline cellulose (MCC) with porosities of 10% and 25%. The terahertz results reveal that the rate of liquid uptake is clearly influenced by the porosity of the tablets with a faster liquid transport observed for tablets with higher porosity, indicating that the samples exhibit structural similarity in respect to pore connectivity and pore size distribution characteristics in respect to permeability. The swelling of the FCC based tablets is fully controlled by the amount of disintegrant, whereas the liquid uptake is driven by the FCC material and the interparticle pores created during compaction. The MCC based formulations are more complex as the MCC significantly contributes to the overall tablet swelling. An increase in swelling with increasing porosity is observed in these tablets, which indicates that such formulations are performance-limited by their ability to take up liquid. Investigating the effect of the microstructure characteristics on the liquid transport and swelling kinetics is of great importance for reaching the next level of understanding of the drug delivery, and, depending on the surface nature of the pore carrier function, in turn controlling the performance of the drug mainly in respect to dissolution in the body.

On optical sensing of surface roughness of flat and curved microplastics in water.

The growth of microplastic (MP) pollution is of increasing concern and represents a global challenge. In situ detection of these small particles is difficult because of their sizes, shapes, transparency or translucency, surface texture and ambient conditions. We propose and demonstrate the use of a prototype optical sensor to detect flat, nearly flat, curved and rough MPs prepared from commercial polyethylene terephthalate (PET) plastics and PET bottles in water. The prototype measures the specular reflection of a laser radiation incident on MPs, with a photodiode, and the transmitted laser speckle pattern, with a charge-coupled device (CCD) camera. The presence of the MPs as well as the optical surface roughness are determined from the specular reflection. Additionally, the so-called speckle contrast calculated from the speckle pattern, as a promising tool, is used to rank the rough MPs according to the different average surface roughness, to approximately twice the wavelength of the probing light. The novel application of laser speckle contrast and the optical roughness estimation allows the description of MP surface roughness in water. Moreover, in combination with earlier studies, these results, therefore, pave a way for the complete and a relatively easier description of MPs properties optical and also advances our step towards the development of simple and robust optical monitoring techniques for micro and nanoplastics in open and wastewater.

Optical screening for presence of banned Sudan III and Sudan IV dyes in edible palm oils.

Due to the proven carcinogenicity of Sudan III and IV dyes, they are considered global public health issues. They are banned in all forms as food colourants. We propose the monitoring of simple and easy-to-measure optical properties of palm oils, such as the refractive indices and spectrophotometric properties, as efficient indicators to detect adulteration. Coupling these results with principal component analysis, excess refractive index, and integration of transmittance introduces a novel detection tool for the authentication of edible palm oil. This opens a new opportunity for accurate handheld devices to detect adulteration and provide control in the field. This work assessed in total of 49 samples, some collected from different parts of Ghana and others, in-house adulterated samples. The Ghana Food and Drugs Authority, who performed a complex and expensive chemical analysis of the samples, confirmed our results with good agreement.

Optical transmission spectra study in visible and near-infrared spectral range for identification of rough transparent plastics in aquatic environments.

Erosion of microplastics due to residence time in aquatic environments causes roughening of the microplastic. Unfortunately, currently used measurement methods do not provide information on the surface roughness of the microplastic embedded in water. In this study we propose a novel method by using transmittance to get information on the magnitude of the surface roughness of microplastics and to rank microplastics by thickness. For such a purpose, we studied optical properties such as dispersion, absorption of both plastics and water in the partial spectral range of visible light (Vis), transmission and scattering of light by plastic sheets, as well as, the calculated sample thickness in the Vis region. These were explored for the detection of both smooth and roughened plastic sheets immersed in water. Moreover, by using the transmission spectrum and refractive index of both plastic and water it is possible to estimate the average surface roughness of plastic samples. Our results suggest that the optical properties in the Vis region offer an interesting way for the detection of both rough and smooth plastic sheets and for ranking the type of plastics in an aquatic environment.

A prototype of a portable optical sensor for the detection of transparent and translucent microplastics in freshwater.

Microplastic pollution in water bodies is an alarming problem which needs to be addressed. However, issues such as size, shape and their appearance to light (transparent or translucent) make it difficult to be optically detected. Here, a feasibility study of a portable prototype optical sensor with the capability of measuring simultaneously specular laser light reflection and transmission from microplastic particles is presented. The specular reflection signal and the transmitted interference pattern were recorded with a photodiode and a CCD camera, respectively. With the combination of these two modes of detection, it is possible to screen the type, size, and nonplanarity of two microplastics types, i.e., transparent polyethylene terephthalate (PET) and translucent low-density polyethylene (LDPE), in a volume of freshwater, with high confidence. In principle, the prototype could be used for the detection of both floating microplastics as well as microplastics experiencing sedimentation in natural water bodies, and in water filtration in water treatment plants.

Outlook on optical identification of micro- and nanoplastics in aquatic environments.

Plastic pollution in natural water bodies is an emerging problem that requires quick actions. Recently, the role of micro- and nanoplastics in pollution and health issues has been realized and taken seriously. In this paper, we have studied optical properties, such as NIR spectra and refractive index, of some common plastic materials and present a method and data to screen especially problematic transparent plastics with rough surface in aquatic environments. We also give an outlook of possible optical measurement methods that could be used for detection of micro- and nanoplastics.

Wavelength-dependent excess permittivity as indicator of kerosene in diesel oil.

Adulteration of diesel oil by kerosene is a serious problem because of air pollution resulting from car exhaust gases. The objective of this study was to develop a relatively simple optical measurement and data analysis method to screen low-adulterated diesel oils. For this purpose, we introduce the utilization of refractive index measurement with a refractometer, scanning of visible-near-infrared transmittance, transmittance data inversion using the singly subtractive Kramers-Kronig relation, and exploitation of so-called wavelength-dependent relative excess permittivity. It is shown for three different diesel oil grades, adulterated with kerosene, that the excess permittivity is a powerful measure for screening fake diesel oils. The excess relative permittivity of such binary mixtures also reveals hidden spectral fingerprints that are neither visible in dispersion data alone nor in spectral transmittance measurements alone. We believe that the excess permittivity data are useful in the case of screening adulteration of diesel oil by kerosene and can further be explored for practical sensing solutions, e.g., in quality inspection of diesel oils in refineries.

Hand-Held Refractometer-Based Measurement and Excess Permittivity Analysis Method for Detection of Diesel Oils Adulterated by Kerosene in Field Conditions.

Adulteration of fuels is a major problem, especially in developing and third world countries. One such case is the adulteration of diesel oil by kerosene. This problem contributes to air pollution, which leads to other far-reaching adverse effects, such as climate change. The objective of this study was to develop a relatively easy measurement method based on an inexpensive, handheld Abbe refractometer for the detection of adulteration and estimation of the ascending order of the amount of kerosene present in adulterated samples in field conditions. We achieved this by increasing the volume of pure diesel sample in the adulterated diesel oil, and measuring the trend of refractive index change, and next, exploiting the true and ideal permittivities of the binary mixture. The permittivity can be obtained with the aid of the measured refractive index of a liquid. Due to the molecular interactions, the true and ideal permittivities of diesel⁻kerosene binary liquid mixture have a mismatch which can be used to screen for adulterated diesel oils. The difference between the true and the ideal permittivity is the so-called excess permittivity. We first investigated a training set of diesel oils in laboratory in Finland, using the accurate table model Abbe refractometer and depicting the behavior of the excess permittivity of the mixture of diesel oil and kerosene. Then, we measured same samples in the laboratory using a handheld refractometer. Finally, preliminary field measurements using the handheld device were performed in Tanzania to assess the accuracy and possibility of applying the suggested method in field conditions. We herein show that it is not only possible to detect even relatively low adulteration levels of diesel in kerosene-namely, 5%, 10%, and 15%-but also it is possible to monitor the ascending order of adulteration for different adulterated diesel samples. We propose that the method of increasing the volume of an unknown (suspected) diesel oil sample by adding a known authentic diesel sample and monitoring excess permittivity is useful for the screening of adulterated diesel oil in field measurement conditions.

Investigating elastic relaxation effects on the optical properties of functionalised calcium carbonate compacts using optics-based Heckel analysis.

Heckel analysis is a widely used method for the characterisation of the compression behaviour of pharmaceutical samples during the preparation of solid dosage formulations. The present study introduces an optical version of the Heckel equation that is based on a combination of the conventional Heckel equation together with the linear relationship defined between the effective terahertz (THz) refractive index and the porosity of pharmaceutical tablets. The proposed optical Heckel equation allows us to, firstly, calculate the zero-porosity refractive index, and, secondly, predict the in-die development of the effective refractive index as a function of the compressive pressure during tablet compression. This was demonstrated for five batches of highly porous functionalised calcium carbonate (FCC) excipient compacts. The close match observed between the estimated in-die effective refractive index and the measured/out-of-die effective THz refractive index supports the validity of the proposed form of the equation. By comparing the measured and estimated in-die tablet properties, a clear change in the porosity and hence, the effective refractive index, due to post-compression elastic relaxation of the FCC compacts, has been observed. We have, therefore, proposed a THz-based compaction setup that will permit in-line monitoring of processes during tablet compression. We envisage that this new approach in tracking powder properties introduced in this preliminary study will lead to the onset of further extensive and detailed future studies.

Characterisation of pore structures of pharmaceutical tablets: A review.

Traditionally, the development of a new solid dosage form is formulation-driven and less focus is put on the design of a specific microstructure for the drug delivery system. However, the compaction process particularly impacts the microstructure, or more precisely, the pore architecture in a pharmaceutical tablet. Besides the formulation, the pore structure is a major contributor to the overall performance of oral solid dosage forms as it directly affects the liquid uptake rate, which is the very first step of the dissolution process. In future, additive manufacturing is a potential game changer to design the inner structures and realise a tailor-made pore structure. In pharmaceutical development the pore structure is most commonly only described by the total porosity of the tablet matrix. Yet it is of great importance to consider other parameters to fully resolve the interplay between microstructure and dosage form performance. Specifically, tortuosity, connectivity, as well as pore shape, size and orientation all impact the flow paths and play an important role in describing the fluid flow in a pharmaceutical tablet. This review presents the key properties of the pore structures in solid dosage forms and it discusses how to measure these properties. In particular, the principles, advantages and limitations of helium pycnometry, mercury porosimetry, terahertz time-domain spectroscopy, nuclear magnetic resonance and X-ray computed microtomography are discussed.

Fast and non-destructive pore structure analysis using terahertz time-domain spectroscopy.

Pharmaceutical tablets are typically manufactured by the uni-axial compaction of powder that is confined radially by a rigid die. The directional nature of the compaction process yields not only anisotropic mechanical properties (e.g. tensile strength) but also directional properties of the pore structure in the porous compact. This study derives a new quantitative parameter, Sa, to describe the anisotropy in pore structure of pharmaceutical tablets based on terahertz time-domain spectroscopy measurements. The Sa parameter analysis was applied to three different data sets including tablets with only one excipient (functionalised calcium carbonate), samples with one excipient (microcrystalline cellulose) and one drug (indomethacin), and a complex formulation (granulated product comprising several excipients and one drug). The overall porosity, tablet thickness, initial particle size distribution as well as the granule density were all found to affect the significant structural anisotropies that were observed in all investigated tablets. The Sa parameter provides new insights into the microstructure of a tablet and its potential was particularly demonstrated for the analysis of formulations comprising several components. The results clearly indicate that material attributes, such as particle size and granule density, cause a change of the pore structure, which, therefore, directly impacts the liquid imbibition that is part of the disintegration process. We show, for the first time, how the granule density impacts the pore structure, which will also affect the performance of the tablet. It is thus of great importance to gain a better understanding of the relationship of the physical properties of material attributes (e.g. intragranular porosity, particle shape), the compaction process and the microstructure of the finished product.

On the role of API in determining porosity, pore structure and bulk modulus of the skeletal material in pharmaceutical tablets formed with MCC as sole excipient.

The physical properties and mechanical integrity of pharmaceutical tablets are of major importance when loading with active pharmaceutical ingredient(s) (API) in order to ensure ease of processing, control of dosage and stability during transportation and handling prior to patient consumption. The interaction between API and excipient, acting as functional extender and binder, however, is little understood in this context. The API indomethacin is combined in this study with microcrystalline cellulose (MCC) at increasing loading levels. Tablets from the defined API/MCC ratios are made under conditions of controlled porosity and tablet thickness, resulting from different compression conditions, and thus compaction levels. Mercury intrusion porosimetry is used to establish the accessible pore volume, pore size distribution and, adopting the observed region of elastic intrusion-extrusion at high pressure, an elastic bulk modulus of the skeletal material is recorded. Porosity values are compared to previously published values derived from terahertz (THz) refractive index data obtained from exactly the same tablet sample sets. It is shown that the elastic bulk modulus is dependent on API wt% loading under constant tablet preparation conditions delivering equal dimensions and porosity. The findings are considered of novel value in respect to establishing consistency of tablet production and optimisation of physical properties.

Optics-based compressibility parameter for pharmaceutical tablets obtained with the aid of the terahertz refractive index.

The objective of this study is to propose a novel optical compressibility parameter for porous pharmaceutical tablets. This parameter is defined with the aid of the effective refractive index of a tablet that is obtained from non-destructive and contactless terahertz (THz) time-delay transmission measurement. The optical compressibility parameter of two training sets of pharmaceutical tablets with a priori known porosity and mass fraction of a drug was investigated. Both pharmaceutical sets were compressed with one of the most commonly used excipients, namely microcrystalline cellulose (MCC) and drug Indomethacin. The optical compressibility clearly correlates with the skeletal bulk modulus determined by mercury porosimetry and the recently proposed terahertz lumped structural parameter calculated from terahertz measurements. This lumped structural parameter can be used to analyse the pattern of arrangement of excipient and drug particles in porous pharmaceutical tablets. Therefore, we propose that the optical compressibility can serve as a quality parameter of a pharmaceutical tablet corresponding with the skeletal bulk modulus of the porous tablet, which is related to structural arrangement of the powder particles in the tablet.

Characterization of the Pore Structure of Functionalized Calcium Carbonate Tablets by Terahertz Time-Domain Spectroscopy and X-Ray Computed Microtomography.

Novel excipients are entering the market to enhance the bioavailability of drug particles by having a high porosity and, thus, providing a rapid liquid uptake and disintegration to accelerate subsequent drug dissolution. One example of such a novel excipient is functionalized calcium carbonate, which enables the manufacture of compacts with a bimodal pore size distribution consisting of larger interparticle and fine intraparticle pores. Five sets of functionalized calcium carbonate tablets with a target porosity of 45%-65% were prepared in 5% steps and characterized using terahertz time-domain spectroscopy and X-ray computed microtomography. Terahertz time-domain spectroscopy was used to derive the porosity using effective medium approximations, that is, the traditional and an anisotropic Bruggeman model. The anisotropic Bruggeman model yields the better correlation with the nominal porosity (R2 = 0.995) and it provided additional information about the shape and orientation of the pores within the powder compact. The spheroidal (ellipsoids of revolution) shaped pores have a preferred orientation perpendicular to the compaction direction causing an anisotropic behavior of the dielectric porous medium. The results from X-ray computed microtomography confirmed the nonspherical shape and the orientation of the pores, and it further revealed that the anisotropic behavior is mainly caused by the interparticle pores. The information from both techniques provides a detailed insight into the pore structure of pharmaceutical tablets. This is of great interest to study the impact of tablet microstructure on the disintegration and dissolution performance.

Reflectometric monitoring of the dissolution process of thin polymeric films.

Pharmaceutical thin films are versatile drug-delivery platforms i.e. allowing transdermal, oral, sublingual and buccal administration. However, dissolution testing of thin films is challenging since the commonly used dissolution tests for conventional dosage forms correspond rather poorly to the physiological conditions at the site of administration. Here we introduce a traditional optical reflection method for monitoring the dissolution behavior of thin polymeric films. The substances, e.g. drug molecules, released from the film generate an increase in the refractive index in the liquid medium which can be detected by reflectance monitoring. Thin EUDRAGIT® RL PO poly(ethyl acrylate-co-methyl methacrylate-co trimethylammonioethyl methacrylate chloride) (RLPO) films containing the model drug perphenazine (PPZ) were prepared by spraying on a glass substrate. The glass substrates were placed inside the flow cell in the reflectometer which was then filled with phosphate buffer solution. Dissolution was monitored by measuring the reflectance of the buffer liquid. The method was able to detect the distinctive dissolution characteristics of different film formulations and measured relatively small drug concentrations. In conclusion, it was demonstrated that a traditional optical reflection method can provide valuable information about the dissolution characteristics of thin polymeric films in low liquid volume surroundings.

On the Immersion Liquid Evaporation Method Based on the Dynamic Sweep of Magnitude of the Refractive Index of a Binary Liquid Mixture: A Case Study on Determining Mineral Particle Light Dispersion.

This is a feasibility study of a modified immersion liquid technique for determining the refractive index of micro-sized particles. The practical challenge of the traditional liquid immersion method is to find or produce a suitable host liquid whose refractive index equals that of a solid particle. Usually, the immersion liquid method uses a set of immersion liquids with different refractive indices or continuously mixes two liquids with different refractive indices, e.g., using a pumping system. Here, the phenomenon of liquid evaporation has been utilized in defining the time-dependent refractive index variation of the host liquid. From the spectral transmittance data measured during the evaporation process, the refractive index of a solid particle in the host liquid can be determined as a function of the wavelength. The method was tested using calcium fluoride (CaF2) particles with an immersion liquid mixed from diethyl ether and diffusion pump fluid. The dispersion data obtained were consistent with the literature values thus indicating the proper functioning of the proposed procedure.

Terahertz study on porosity and mass fraction of active pharmaceutical ingredient of pharmaceutical tablets.

In this study, terahertz time-domain spectroscopic (THz-TDS) technique has been used to ascertain the change in the optical properties, as a function of changing porosity and mass fraction of active pharmaceutical ingredient (API), of training sets of pharmaceutical tablets. Four training sets of pharmaceutical tablets were compressed with microcrystalline cellulose (MCC) excipient and indomethacin API by varying either the porosity, height, and API mass fraction or all three tablet parameters. It was observed, as far as we know, for the first time, that the THz time-domain and frequency-domain effective refractive index, as well as, the frequency-domain effective absorption coefficient both show linear correlations with the porosity and API mass fraction for training sets of real pharmaceutical tablets. We suggest that, the observed linear correlations can be useful in basic research and quality inspection of pharmaceutical tablets. Additionally, we propose a novel optical strain parameter, based on THz measurement, which yields information on the conventional strain parameter of a tablet as well as on the change of fill fraction of solid material during compression of porous pharmaceutical tablets. We suggest that the THz measurement and proposed method of data analysis, in addition to providing an efficient tool for basic research of porous media, can serve as one of the novel quality by design (QbD) implementation techniques to predict critical quality attributes (CQA) such as porosity, API mass fraction and strain of flat-faced pharmaceutical tablets before production.

Noninvasive porosity measurement of biconvex tablets using terahertz pulses.

Biconvex pharmaceutical microcrystalline cellulose (MCC) compacts were investigated by the detection of terahertz (THz) pulse delay in the transmission measurement mode. The dimensions of the tablets were kept as constants but the porosity was a priori known variable. It is shown that the porosity of the biconvex compact has a linear correlation with the THz pulse delay. By constructing a calibration line between these two parameters (i.e. porosity and THz pulse delay), it is possible to non-invasively detect porosity of biconvex tablets. We suggest that this preliminary study could be the starting point of in-depth future studies on the screening of porosity and related properties of real biconvex pharmaceutical tablets using terahertz sensing techniques.