Analytical applications of smartphones for agricultural soil analysis.

Soil is one of the most important farming resources. Appropriate managing of its quality promotes productive and sustainable agriculture. The valuable farm practice in soil quality managing is based on regular soil analysis with the aim of determining the exact amount of nutrients or other chemical, physical, and biological soil properties. Soil analysis usually requires sample collection at the desired sampling depth followed by sample delivery to chemical laboratories. However, laboratory analyses are resource-intensive and costly, and require a lot of time, effort, and equipment. A low-cost, fast, and effective alternative for soil quality control is the application of smartphones to perform chemical analyses directly in the field or on the farm. In this paper, an overview of recent developments on smartphone-based methodologies for agricultural purposes and portable evaluation of soil quality and its properties is presented. The discussion focuses on recent applications of smartphone-based devices for the determination of basic soil parameters, content of organic matter, mineral fertilizers, and organic or inorganic pollutants. Obvious advantages of using smartphones, such as convenience and simplicity of use, and the main shortcomings, such as relatively poor precision of the results obtained, are also discussed. The general trend shows the huge interest from researchers to move the technology into the field with the aim of providing cost-effective and rapid soil analysis. This paper can broaden the understanding of using smartphones for chemical analysis of soil samples, as it is a relatively new area and is expected to be developed rapidly.

Development and validation of an eco-compatible UV-Vis spectrophotometric method for the determination of Cu2+ in aqueous matrices.

Cu2+ are ubiquitous ions in the ecosystem and are responsible of serious environmental pollution. Indeed, the development of sensitive methods for Cu2+ detection is an urgent demand. In this work, we proposed a new spectrophotometric method for Cu2+ determination in different water matrices (distilled water, drinking water, wastewater, and river water). The method employs a bio-based organic ligand namely tetrasodium iminodisuccinate (IDS) able to form a stable complex with the analyte with a maximum absorption at 710 nm. Within the linear range of 6.3-381 mg L-1, the limit of detection (LOD) was determined to be as 1.43 mg L-1. Moreover, the recovery data of the spiked analysis of drinking/river/wastewater water samples were also satisfactory and verified the feasibility of the method for the analysis of Cu2+ in natural conditions. Finally, the AGREE assessment tool was used for a quantitative evaluation of the proposed method and reference method, in agreement with the green analytical chemistry principles. The results showed the lower environmental impact of the proposed method and the suitability of this novel approach for Cu2+ in water matrices.

Emissions and toxic units of solvent, monomer and additive residues released to gaseous phase from latex balloons.

This study describes the VOCs emissions from commercially available latex balloons. Nine compounds are determined to be emitted from 13 types of balloons of different colors and imprints in 30 and 60 °C. The average values of total volatile organic compounds (TVOCs) emitted from studied samples ranged from 0.054 up to 7.18 µg g-1 and from 0.27 up to 36.11 µg g-1 for 30 °C and 60 °C, respectively. The dataset is treated with principal component analysis (PCA) and multiple curve resolution (MCR) to characterize its internal patterns. Here two groups on compounds are recognized - the first one related to balloon material, the second one being emissions of compounds previously adsorbed on balloon material. The toxicity assessment of MCR modeled balloons' emissions was performed by toxic unit (TU) approach. The obtained TUs were summed to give toxicity emission assessment. The incorporation of TUs allows to identify the balloons with the most toxic emissions- imprinted ones in 60 °C. The compounds of the highest TUs are hexanal and benzene. FTIR analysis shows that all balloons are made of the same polymeric material - isoprene, so all differences in emissions are related to different additives like pigments, imprints or these responsible for opaqueness. Analyzing the obtained research results it was noticed that latex balloons might be considered as an important source of emission of aliphatic and monoaromatic hydrocarbons to the gaseous phase.

Multicriteria Decision Analysis and Grouping of Analytical Procedures for Phthalates Determination in Disposable Baby Diapers.

This study presents the application of one of the tools from the multicriteria decision analysis set (MCDA), the Technique for Order Preference by Similarity to Ideal Solution (TOPSIS). Selected green analytical chemistry metrics were used to rank analytical procedures for the phthalate determination in disposable baby diapers. Nine analytical procedures were assessed in order to find one that has the lowest environmental impact and the best analytical figures of merit. Nine different criteria, where weighting was based on the experts' evaluation, were used in the procedures' assessment. With the use of TOPSIS, an easy and straightforward technique, selection of the most appropriate procedure was made.

AGREE-Analytical GREEnness Metric Approach and Software.

Green analytical chemistry focuses on making analytical procedures more environmentally benign and safer to humans. The amounts and toxicity of reagents, generated waste, energy requirements, the number of procedural steps, miniaturization, and automation are just a few of the multitude of criteria considered when assessing an analytical methodology's greenness. The use of greenness assessment criteria requires dedicated tools. We propose the Analytical GREEnness calculator, a comprehensive, flexible, and straightforward assessment approach that provides an easily interpretable and informative result. The assessment criteria are taken from the 12 principles of green analytical chemistry (SIGNIFICANCE) and are transformed into a unified 0-1 scale. The final score is calculated based on the SIGNIFICANCE principles. The result is a pictogram indicating the final score, performance of the analytical procedure in each criterion, and weights assigned by the user. Freely available software makes the assessment procedure straightforward. It is open-source and downloadable from https://mostwiedzy.pl/AGREE.

Searching for Solvents with an Increased Carbon Dioxide Solubility Using Multivariate Statistics.

Ionic liquids (ILs) are used in various fields of chemistry. One of them is CO2 capture, a process that is quite well described. The solubility of CO2 in ILs can be used as a model to investigate gas absorption processes. The aim is to find the relationships between the solubility of CO2 and other variables-physicochemical properties and parameters related to greenness. In this study, 12 variables are used to describe a dataset consisting of 26 ILs and 16 molecular solvents. We used a cluster analysis, a principal component analysis, and a K-means hierarchical clustering to find the patterns in the dataset and the discriminators between the clusters of compounds. The results showed that ILs and molecular solvents form two well-separated groups, and the variables were well separated into greenness-related and physicochemical properties. Such patterns suggest that the modeling of greenness properties and of the solubility of CO2 on physicochemical properties can be difficult.

Calculating the Partition Coefficients of Organic Solvents in Octanol/Water and Octanol/Air.

Partition coefficients define how a solute is distributed between two immiscible phases at equilibrium. The experimental estimation of partition coefficients in a complex system can be an expensive, difficult, and time-consuming process. Here a computational strategy to predict the distributions of a set of solutes in two relevant phase equilibria is presented. The octanol/water and octanol/air partition coefficients are predicted for a group of polar solvents using density functional theory (DFT) calculations in combination with a solvation model based on density (SMD) and are in excellent agreement with experimental data. Thus, the use of quantum-chemical calculations to predict partition coefficients from free energies should be a valuable alternative for unknown solvents. The obtained results indicate that the SMD continuum model in conjunction with any of the three DFT functionals (B3LYP, M06-2X, and M11) agrees with the observed experimental values. The highest correlation to experimental data for the octanol/water partition coefficients was reached by the M11 functional; for the octanol/air partition coefficient, the M06-2X functional yielded the best performance. To the best of our knowledge, this is the first computational approach for the prediction of octanol/air partition coefficients by DFT calculations, which has remarkable accuracy and precision.

Analytical chemistry with biosolvents.

One of the current trends in green analytical chemistry is the introduction of green solvents, some of which are biobased. At the same time, the development of the biorefinery concept has allowed more biochemicals to be obtained with increased efficiency and from a wider range of feedstocks. The first examples of the use of biosolvents in analytical applications included extractions performed with alcohols, esters, and terpenes. However, many more applications of biosolvents in extractions of bioactive compounds from various plant materials have also been reported, which hints at a wider range of potential analytical applications of biosolvents. It should also be noted that the biobased solvents applied in analytical chemistry are not always green, as some of them are toxic towards aquatic organisms. Graphical abstract.

How green are ionic liquids? - A multicriteria decision analysis approach.

Due to various desirable physicochemical properties, ionic liquids (ILs) are still gaining in popularity. ILs have been recurrently considered green solvents. However, environmental, health and safety assessments of ILs have raised certain doubts about their benignness, and their greenness status is currently unclear. To clarify the situation on their greenness, we perform a comprehensive assessment of more than 300 commercially available ILs. We apply multicriteria decision analysis, the tool that allows ranking many alternatives according to relevant criteria. They are toxicity towards various organisms, biodegradability, hazard statements and precautionary measures during their handling. We incorporated organic solvents to rankings, as their greenness is better described, so they serve as greenness reference points. The ranking results obtained considering the whole set of criteria show that ILs are placed between recommended polar solvents and problematic/undesirable non polar organic solvents in terms of greenness. However, the exclusion of toxicity data due to unavailability of endpoints results in assessment of ILs as greener than most of organic solvents.

Pre-selection and assessment of green organic solvents by clustering chemometric tools.

The study presents the result of the application of chemometric tools for selection of physicochemical parameters of solvents for predicting missing variables - bioconcentration factors, water-octanol and octanol-air partitioning constants. EPI Suite software was successfully applied to predict missing values for solvents commonly considered as "green". Values for logBCF, logKOW and logKOA were modelled for 43 rather nonpolar solvents and 69 polar ones. Application of multivariate statistics was also proved to be useful in the assessment of the obtained modelling results. The presented approach can be one of the first steps and support tools in the assessment of chemicals in terms of their greenness.

Expectation-Maximization Model for Substitution of Missing Values Characterizing Greenness of Organic Solvents.

Organic solvents are ubiquitous in chemical laboratories and the Green Chemistry trend forces their detailed assessments in terms of greenness. Unfortunately, some of them are not fully characterized, especially in terms of toxicological endpoints that are time consuming and expensive to be determined. Missing values in the datasets are serious obstacles, as they prevent the full greenness characterization of chemicals. A featured method to deal with this problem is the application of Expectation-Maximization algorithm. In this study, the dataset consists of 155 solvents that are characterized by 13 variables is treated with Expectation-Maximization algorithm to predict missing data for toxicological endpoints, bioavailability, and biodegradability data. The approach may be particularly useful for substitution of missing values of environmental, health, and safety parameters of new solvents. The presented approach has high potential to deal with missing values, while assessing environmental, health, and safety parameters of other chemicals.

Hasse diagram as a green analytical metrics tool: ranking of methods for benzo[a]pyrene determination in sediments.

This study presents an application of the Hasse diagram technique (HDT) as the assessment tool to select the most appropriate analytical procedures according to their greenness or the best analytical performance. The dataset consists of analytical procedures for benzo[a]pyrene determination in sediment samples, which were described by 11 variables concerning their greenness and analytical performance. Two analyses with the HDT were performed-the first one with metrological variables and the second one with "green" variables as input data. Both HDT analyses ranked different analytical procedures as the most valuable, suggesting that green analytical chemistry is not in accordance with metrology when benzo[a]pyrene in sediment samples is determined. The HDT can be used as a good decision support tool to choose the proper analytical procedure concerning green analytical chemistry principles and analytical performance merits.

Scoring of solvents used in analytical laboratories by their toxicological and exposure hazards.

Green analytical chemistry, although a well recognised concept, still lacks reliable environmental impact assessment procedures. This article describes scoring of solvents, frequently used in analytical laboratories, with CHEMS-1 model. The model uses toxicological and exposure data to calculate hazard values related to the utilisation of solvents. The original model was modified to incorporate hazards related to the volatility of chemicals. The scoring of hazard values showed that polar solvents are less hazardous. The scoring results were applied to assess the total hazard values in terms of solvent consumption. The hazard scores calculated for each chemical were multiplied by the volumes of solvent used during the analytical procedure. The results show that calculation of total procedural hazard values is valuable in the green analytical chemistry assessment procedure. Moreover, the assessment procedure can be combined with other procedural greenness assessment methods.

Green Chemistry Metrics with Special Reference to Green Analytical Chemistry.

The concept of green chemistry is widely recognized in chemical laboratories. To properly measure an environmental impact of chemical processes, dedicated assessment tools are required. This paper summarizes the current state of knowledge in the field of development of green chemistry and green analytical chemistry metrics. The diverse methods used for evaluation of the greenness of organic synthesis, such as eco-footprint, E-Factor, EATOS, and Eco-Scale are described. Both the well-established and recently developed green analytical chemistry metrics, including NEMI labeling and analytical Eco-scale, are presented. Additionally, this paper focuses on the possibility of the use of multivariate statistics in evaluation of environmental impact of analytical procedures. All the above metrics are compared and discussed in terms of their advantages and disadvantages. The current needs and future perspectives in green chemistry metrics are also discussed.

Smartphone-based digital image colorimetry for the determination of total capsaicinoid content in chili pepper extracts.

A simple smartphone-based digital image colorimetry was proposed for the determination of total capsaicinoid content and the assessment of chili pepper pungency. The biobased solvent D-limonene was used for the first time to isolate analytes. Capsaicinoids were efficiently separated from chili pepper by solid-liquid extraction with D-limonene followed by partitioning of the analytes into the ammonium hydroxide solution to eliminate the matrix interference effect. For colorimetric detection of total capsaicinoid content, a selective chromogenic reaction was performed using Gibbs reagent (2,6-dichloroquinone-4-chloroimide). Measurements were performed using a smartphone-based setup and included image analysis with the program ImageJ. The limit of detection of the proposed procedure was 0.15 mg g-1. The intra-day repeatability did not exceed 10.0 %. The inter-day repeatability was less than 16.5 %. The comparison of the smartphone-based procedure with high-performance liquid chromatography showed satisfactory results.

Simple smartphone-based methods for the determination of bioactive compounds in wine.

A set of simple smartphone-based methods of bioactive compounds determination were developed for wine analysis. Procedures for smartphone-based determination of the total content of phenolic compounds, flavonoids, anthocyanins and biogenic amines, as well as measurement of antioxidant activity were developed and fully validated. The experimental setup is based on smartphone and 3D-printed device, though it is very simple and can be conveniently applied in lab and in field. The proposed solutions have satisfactory figures of merit with R2 in the range of 0.9860-0.9981 for linear range. The recoveries were in range 98.6-102%, RSDs up to 4.2% and LODs below 2.3 mg/L. In order to demonstrate the applicability of the proposed procedures, wine samples were analysed using spectrophotometry and newly developed methods. The results of application of smartphone and spectrophotometer are comparable, in terms of validation parameters and measured concentrations in real samples.

AGREEMIP: The Analytical Greenness Assessment Tool for Molecularly Imprinted Polymers Synthesis.

Molecular imprinting technology is well established in areas where a high selectivity is required, such as catalysis, sensing, and separations/sample preparation. However, according to the Principles of Green Chemistry, it is evident that the various steps required to obtain molecularly imprinted polymers (MIPs) are far from ideal. In this regard, greener alternatives to the synthesis of MIPs have been proposed in recent years. However, although it is intuitively possible to design new green MIPs, it would be desirable to have a quantitative measure of the environmental impact of the changes introduced for their synthesis. In this regard, this work proposes, for the first time, a metric tool and software (termed AGREEMIP) to assess and compare the greenness of MIP synthesis procedures. AGREEMIP is based on 12 assessment criteria that correspond to the greenness of different reaction mixture constituents, energy requirements, and the details of MIP synthesis procedures. The input data of the 12 criteria are transformed into individual scores on a 0-1 scale that in turn produce an overall score through the calculation of the weighted average. The assessment can be performed using user-friendly open-source software, freely downloadable from mostwiedzy.pl/agreemip. The assessment result is an easily interpretable pictogram and visually appealing, showing the performance in each of the criteria, the criteria weights, and overall performance in terms of greenness. The application of AGREEMIP is presented with selected case studies that show good discrimination power in the greenness assessment of MIP synthesis pathways.

Green, simple analytical method for total biogenic amines content determination in wine using spectrophotometry.

A simple, green and equitable procedure for total biogenic amines (BAs) content determination was developed. The scientific novelty lies in the use of commercially available S0378 dye, the reaction of which with BAs results in a colour change of the solution. Sample preparation and analysis were simplified to make the method suitable for routine analyses even in resource-scarce settings. The optimization of the method was carried out using a Box-Behnken response surface design. The developed method has satisfactory figures of merit for putrescine equivalent determination with R2 in the range of 0.9906-0.9933 and recovery between 99.7 and 101.2%. The method's greenness was assessed using AGREEprep. Finally, wine samples were analysed to demonstrate the applicability of the developed method.

Simple analytical method for total biogenic amines content determination in wine using a smartphone.

A simple, fast, and green smartphone-based procedure for total biogenic amines content determination in wine was developed and validated. Sample preparation and analysis were simplified to make the method suitable for routine analyses even in resource-scarce settings. The commercially available S0378 dye and smartphone-based detection were used for this purpose. The developed method has satisfactory figures of merit for putrescine equivalent determination with R2 of 0.9981. The method's greenness was also assessed using the Analytical Greenness Calculator. Samples of Polish wine were analysed to demonstrate the applicability of the developed method. Finally, results obtained with the developed procedure were compared with those previously obtained with GC-MS in order to evaluate the equivalence of the methods.

Determination of chlorinated solvents in industrial water and wastewater by DAI-GC-ECD.

A very simple and quick analytical method, based on direct aqueous injection, for determination of halogenated solvents in refinery water and wastewater, is described. There is a need to determine halogenated solvents in refinery water streams, because they may originate from several processes. There is also a need to develop methods enabling VOX to be determined in samples containing oil fractions. The method described enables simultaneous determination of 26 compounds with low detection limits (sub-µg L(-1)) and excellent precision, especially for highly halogenated solvents. The matrix effects of four types of sample were evaluated--the method seemed to be relatively insensitive to variations in matrix composition. Deuterated 1,2-dichloroethane was used as internal standard and surrogate compound in quantitative analysis; application of isotopically labelled compounds is rarely reported when non-mass spectrometric detectors are used for analysis. Analysis of real samples showed that the most frequently detected compounds were dichloromethane and 1,2-dichloroethane.