Food process contaminants: formation, occurrence, risk assessment and mitigation strategies - a review.

Thermal treatment of food can lead to the formation of potentially harmful chemicals, known as process contaminants. These are adventitious contaminants that are formed in food during processing and preparation. Various food processing techniques, such as heating, drying, grilling, and fermentation, can generate hazardous chemicals such as acrylamide (AA), advanced glycation end products (AGEs), heterocyclic aromatic amines (HAAs), furan, polycyclic aromatic hydrocarbons (PAHs), N-nitroso compounds (NOCs), monochloropropane diols (MCPD) and their esters (MCPDE) which can be detrimental to human health. Despite efforts to prevent the formation of these compounds during processing, eliminating them is often challenging due to their unknown formation mechanisms. It is critical to identify the potential harm to human health in processed food and understand the mechanisms by which harmful compounds form during processing, as prolonged exposure to these toxic compounds can lead to health problems. Various mitigation strategies, such as the use of diverse pre- and post-processing treatments, product reformulation, additives, variable process conditions, and novel integrated processing techniques, have been proposed to control these food hazards. In this review, we summarize the formation and occurrence, the potential for harm to human health produced by process contaminants in food, and potential mitigation strategies to minimize their impact.

Metals, nonmetals and metalloids in cigarette smoke as hazardous compounds for human health.

Cigarette smoke contains many chemicals that are harmful to both smokers and non-smokers. Breathing just a little cigarette smoke can be harmful. There are >7000 chemicals in cigarette smoke, at least 250 are known to be harmful and many of them can cause cancer. Currently, many studies reported the types of harmful organic compounds in cigarette smoke; instead, there are almost no works that describe the presence of inorganic compounds. In this work, a cost-effective self-made passive sampler (SMPS) was tested as a tool to collect different types of particulate matter (PM) from cigarette smoke containing metals as hazardous compounds (HCs). To determine the nature of the metals, nonmetals and metalloids as HCs, a direct qualitative analysis of the particulate matter (PM) was conducted without developing any special sample preparation procedure. For that, non-invasive elemental (Scanning Electron Microscope coupled to Energy Dispersive X-ray Spectrometry) and molecular (Raman microscopy) micro-spectroscopic techniques were used. Thanks to this methodology, it was possible to determine in deposited PM, the presence of metals such as Fe, Cr, Ni, Ti, Co, Sn, Zn, Ba, Al, Cu, Zr, Ce, Bi, etc. most of them as oxides but also embedded in different clusters with sulfates, aluminosilicates, even phosphates.

Health Benefits, Antioxidant Activity, and Sensory Attributes of Selected Cold-Pressed Oils.

The consumption of cold-pressed oils (CPOs) has continuously increased due to their health-promoting compounds, such as polyunsaturated fatty acid (PUFA), tocopherols, sterols, and polyphenols. This study focused on the estimation and comparison of the physicochemical properties and sensory quality of six CPOs: linseed oil (CPLO), pumpkin oil (CPPO), milk thistle oil (CPMTO), rapeseed oil (CPRO), camelina oil (CPCO), and sunflower oil (CPSO), which are the most popular in the Polish market. These oils were analysed for their fatty acid composition (FAC), their tocopherol, sterol, polycyclic aromatic hydrocarbon (PAHs), water, and volatile matter (WVM) contents, as well as their antioxidant activity (AA) and oxidative stability parameters. Moreover, quantitative descriptive analysis (QDA) was performed to obtain detailed information on the sensory profiles and quantitative data on the CPOs' attributes that affected consumer acceptability and purchase intent. All of the analysed CPOs were rich in PUFA (27.94-68.42%). They were characterised by the different total amounts of health-beneficial compounds, such as tocopherols (TTC = 44.04-76.98 mg/100 g), sterols (TSC = 300-684 mg/100 g), and polyphenols (TPC = 2.93-8.32 mg GA/100 g). Additionally, their AA was determined using 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), and ferric reducing antioxidant power (FRAP) methods, with results ranging between 185.36-396.63, 958.59-1638.58, and 61.93-119.21 µmol TE/100 g, respectively. However, the deterioration parameters of CPOs, such as peroxide values (PV = 0.24-4.61 meq O2/kg), p-anisidine values (pAnV = 0.39-4.77), acid values (AV = 0.31-2.82 mg KOH/g), and impurity amounts (Σ4PAHs = 1.16-8.76 µg/kg and WVM = 0.020-0.090%), did not exceed the level recommended by the Codex Alimentarius Commission. The obtained results indicated that all of the investigated CPOs are valuable sources of health-promoting bioactive compounds.

Liquid Phase Microextraction of Hazardous Compounds in Dairy Products; Principal and Practical Aspects.

Liquid phase microextraction techniques are considered as the miniaturized version of traditional liquid-liquid extraction, which use only several microliters of a proper solvent to extract the analytes from sample. In these methods, the target analytes are migrated into a water-immiscible organic solvent (acceptor phase) from an aqueous sample (donor phase). They are mainly classified into three main groups including (a) single-drop microextraction, (b) dispersive liquid-liquid microextraction, and (c) hollow fiber-liquid phase microextraction. These techniques have been successfully applied to the assessment of different analytes in food samples, pharmaceuticals, beverages, and so on. This review mainly focuses on up-to-date information on the application of liquid phase microextraction techniques in dairy products. The advantages and disadvantages of the developed liquid phase microextraction methods were discussed.

Simultaneous evaluation of benzotriazoles, benzothiazoles and benzenesulfonamides in water samples from the impacted urban Jacarepaguá Lagoon System (Rio de Janeiro, Brazil) by liquid chromatography coupled to electrospray tandem mass spectrometry.

Benzotriazoles, benzothiazoles, and benzenesulfonamides are emerging pollutants stable in aquatic media emitted by anthropogenic sources. Selected compounds of these classes were evaluated in the impacted urban Jacarepaguá Lagoon System (JLS) located in a tropical coastal region of Rio de Janeiro City, Brazil that has experienced a rapid expansion of urban occupation and environmental degradation in recent decades, and it represents a pioneering study of these compounds carried out in Brazilian areas. A method of solid phase extraction followed by ultra-performance liquid chromatography coupled to electrospray tandem mass-spectrometry was implemented to evaluate water samples collected in different water bodies (rivers, lagoons, and channels) of the JLS from March 2017 to May 2018. Limits of quantification (LOQs) ≤ 10.0 ng L-1, method linearity up to 1000 µg L-1, and recoveries between 62 and 121 % at three different levels were obtained. Individual concentrations varied from < LOQ to 5260 ng L-1 (benzotriazole, in May 2018) which also predominated in all river samples. 2-mercaptobenzothiazole predominated in samples taken in lagoons and channels in March 2017, and 2-aminobenzothiazole was never detected. River samples showed total concentrations up to 30 times larger in all sampling campaigns, except March 2017 when the sample taken at Tijuca Lagoon showed the largest total concentration of the compounds studied due to the largest concentration of 2-mercaptobenzothiazole (2505 ng L-1) found in this study. Principal component analysis (PCA) using only composition data was unable to distinguish samples from rivers, and lagoons and channels, but a PCA combining composition data and environmental parameters (pH, Eh, dissolved O2 concentration, temperature, salinity, and conductivity) discriminated the samples according to two groups: rivers and lagoons and channels. The Joá Channel flows directly to the open sea and our data allowed a (preliminary) estimation of the total mass flows of the studied compounds to the open sea, which would vary between 1702 g day-1 (March 2017) to 106 g day-1 (May 2018) and allowed a preliminary estimative based on the geometric mean of input of 87.9 kg year-1, indicating the importance of the drainage area to the contamination of the coastal area, and consequently to ocean pollution.

Green methodology based on active air sampling followed by solid phase microextraction and gas chromatography-tandem mass spectrometry analysis to determine hazardous substances in different environments related to tire rubber.

A fast, efficient, and simple air sampling methodology was developed to study a high number of volatile and semivolatile organic compounds in air above tire rubber materials and surfaces made of recycled tire rubber. The proposed method, based on active sampling (solid-phase extraction, SPE) using a small quantity of sorbent material (25 mg) followed by solid-phase microextraction (SPME) and gas chromatography-tandem mass spectrometry analysis, was developed with the aim of determining 40 organics substances including polycyclic aromatic hydrocarbons (PAHs), plasticizers, antioxidants, and vulcanization agents. An experimental design was carried out to study the influence of main factors such as type of SPME fibre, solvent addition, headspace volume, stirring, as well as the factor interactions. Method performance showed good linearity in a broad concentration range (0.05 to 200 ng m-3, for most compounds), with coefficients of determination (R2) higher than 0.9900. Whole method precision (≤ 16 %) and accuracy were also satisfactory, obtaining quantitative recoveries (mean values between 80 and 110 % in most cases). Limits of detection and quantification have also been calculated, yielding values of sub ng m-3 for most compounds. The validated method was applied to outdoor and indoor air environments including playgrounds, football pitches and warehouses showing the presence of most target compounds in the samples achieving high levels for some PAHs (concentrations up to 51 ng m-3), benzothiazole (BTZ), diisobutyl- dibutyl- and di-(2-ethylhexyl)- phthalate, among others, reaching concentrations up to hundreds of ng m-3 (BTZ). This is the first time that the combination of techniques SPE and SPME is applied for these families of chemicals, and it is also the first time that this approach is proposed for the simultaneous multiclass compound extraction of substances of different chemical families. The whole sampling and extraction procedure is performed in a short period of time (61 min) allowing high throughput. The elimination of the use of organic solvents and waste generation by using only 25 mg of sorbent and a SPME fibre than are both reused makes the method sustainable and in consonance with the principles of the green chemistry. The method can be implemented in any routine lab and easily automated using a SPME autosampler.

Lignin peroxidase in focus for catalytic elimination of contaminants - A critical review on recent progress and perspectives.

Lignin peroxidase (LiP) seems to be a catalyst for cleaving high-redox potential non-phenolic compounds with an oxidative cleavage of CC and COC bonds. LiP has been picked to seek a practical and cost-effective alternative to the sustainable mitigation of diverse environmental contaminants. LiP has been an outstanding tool for catalytic cleaning and efficient mitigation of environmental pollutants, including lignin, lignin derivatives, dyes, endocrine-disrupting compounds (EDCs), and persistent organic pollutants (POPs) for the past couple of decades. The extended deployment of LiP has proved to be a promising method for catalyzing these environmentally related hazardous pollutants of supreme interest. The advantageous potential and capabilities to act at different pH and thermostability offer its working tendencies in extended environmental engineering applications. Such advantages led to the emerging demand for LiP and increasing requirements in industrial and biotechnological sectors. The multitude of the ability attributed to LiP is triggered by its stability in xenobiotic and non-phenolic compound degradation. However, over the decades, the catalytic activity of LiP has been continuing in focus enormously towards catalytic functionalities over the available physiochemical, conventional, catalyst mediated technology for catalyzing such molecules. To cover this literature gap, this became much more evident to consider the catalytic attributes of LiP. In this review, the existing capabilities of LiP and other competencies have been described with recent updates. Furthermore, numerous recently emerged applications, such as textile effluent treatment, dye decolorization, catalytic elimination of pharmaceutical and EDCs compounds, have been discussed with suitable examples.

Removal of Organic Compounds with an Amino Group during the Nanofiltration Process.

The research covered the process of nanofiltration of low molecular weight organic compounds in aqueous solution. The article presents the results of experiments on membrane filtration of compounds containing amino groups in the aromatic ring and comparing them with the results for compounds without amino groups. The research was carried out for several commercial polymer membranes: HL, TS40, TS80, DL from various manufacturers. It has been shown that the presence of the amino group and its position in relation to the carboxyl group in the molecule affects the retention in the nanofiltration process. The research also included the oxidation products of selected pharmaceuticals. It has been shown that 4-Amino-3,5-dichlorophenol-a oxidation product of diclofenac and 4-ethylbenzaldehyde-a oxidation product of IBU, show poor separation efficiency on the selected commercial membranes, regardless of the pH value and the presence of natural organic matter (NOM). It has been shown that pre-ozonation of natural river water can improve the retention of pollutants removed.

Effects of Cooking Cycle Times of Marinating Juice and Reheating on the Formation of Cholesterol Oxidation Products and Heterocyclic Amines in Marinated Pig Hock.

In this work the effects of cooking cycle times of marinating juice and reheating on the formation of cholesterol oxidation products (COPs) and heterocyclic amines (HAs) in marinated pig hock were investigated. After the 12th cycle, the total content of COPs was 3.3, 2.0, and 2.0 times higher than that after the 1st cycle in the skin, subcutaneous fat, and lean meat, respectively. The total content of HAs was 5.8, 6.0, and 5.6 times higher than that after the 1st cycle in the skin, subcutaneous fat, and lean meat, respectively. Notably, more COPs were present in the lean meat than in the skin and subcutaneous fat, whereas the content of HAs in the skin was the highest. Compared with the unreheated samples, the total content of COPs and HAs in all tissues increased after reheating at 95 °C for 30 min or at 121 °C for 25 min, but no significant difference was found between different reheating conditions.

Determination of 14 heterocyclic aromatic amines in meat products using solid-phase extraction and supercritical fluid chromatography coupled to triple quadrupole mass spectrometry.

A novel, simple, and sensitive method has been developed for simultaneous determination of 14 heterocyclic aromatic amines in meat product using solid-phase extraction combined with ultrahigh-performance supercritical fluid chromatography coupled to tandem quadrupole mass spectrometry. The analytes could be separated within 7 min and identified using their retention times and mass. The developed method was validated based on the linearity, limits of quantification, precision, and accuracy. The recovery ranged from 52.3 to 97.5% with an acceptable standard deviation, which is not higher than 6%. The limits of quantitation ranged from 0.03 to 0.17 µg/kg. The selectivity and sensitivity were satisfactory in multiple reaction monitoring mode. The method was applied to commercial meat products, and the results demonstrated that the novel method has potential for the analysis of the targets in food matrices. This is the first work reporting the simultaneous quantification of 14 heterocyclic aromatic amines by means of ultrahigh-performance supercritical fluid chromatography coupled to tandem quadrupole mass spectrometry.

An insight into toxicity and human-health-related adverse consequences of cosmeceuticals - A review.

In recent years, the use of cosmeceutical-based personal care and beauty products has ever increased, around the world. Currently, an increasing number of compounds are being assimilated in the formulation of cosmetic products as preservatives, fragrances, surfactants, etc. to intensify the performance, quality, value, and lifespan of cosmetics. Nevertheless, many of these chemical additives pose toxic effects to the human body, exhibiting health risks from a mild hypersensitivity to life-threatening anaphylaxis or lethal intoxication. Therefore, the indiscriminate application of cosmeceuticals has recently become a mounting issue confronting public health. The present review focuses on exposure to a large variety of toxic substances used in cosmetic formulations such as 1,4-dioxane formaldehyde, paraformaldehyde, benzalkonium chloride, imidazolidinyl urea, diazolidinyl urea, trace heavy metals, parabens derivatives, phthalates, isothiazolinone derivatives (methylchloroiso-thiazolinone, and methylisothiazolinone), methyldibromo glutaronitrile, and phenoxy-ethanol. The biological risks related to these substances that they can pose to human health in terms of cytotoxicity, genotoxicity, mutagenicity, neurotoxicity oestrogenicity or others are also discussed. Researchers from academia, consultancy firms, governmental organizations, and cosmetic companies should carry out further progress to keep updating the consumers regarding the dark-sides, and health-related harmful apprehensions of cosmetics. In addition, the industry-motivated initiatives to abate environmental impact through green, sustainable and eco-friendly product development grasp significant perspective.

Study of chemical composition and nutritional values of vegetable wastes in Bangladesh.

The present study was conducted with the objectives of determining the chemical composition and nutritional value of vegetable waste (VW) of households and the marketplace for their suitability as ruminant feed. The crude protein, total digestible nutrients and extent of rumen degradability of dry matter (DM) of VW of households were 140.0 g kg-1, 0.668 and 0.855, respectively; while those of the marketplace were 169.0 g kg-1, 0.633 and 0.80, respectively. The levels of chromium and lead in each respectively, was 13.27 and 1.53 ng kg-1DM; and 31.01 and 5.71 ng kg-1DM. The total aflatoxins in VW of households was 3.08 µg kg-1DM, and undetectable in VW from the marketplace. Considering the chemical composition and safety parameters studied, VW could preliminary be considered as animal feed. The feeding of processed marketplace VW (VWP) at 275 g kg-1DM of a diet or 0.76% of live weight (LW) to growing bulls, replacing 50% of a concentrate mixture as supplement to a Napier silage diet for a period of 34 days reduced the total DM intake (0.0276 vs 0.0343 LW) without any significant (P > 0.05) changes in DM or protein digestibility. Blood urea levels (19.5 vs 23.67 mg dl-1), and serum creatinine levels (1.37 vs 1.08 mg dl-1) differed significantly (P > 0.05) between the two groups but were within normal physiological ranges. Therefore, it may be concluded that the level of incorporation of VWP would be less than 50% replacement of the concentrate in the diet. Further research is required to determine optimum inclusion levels in ruminant diets.

Metallurgical residues reused as filler after 35years and their natural weathering implications in a mountain area.

The natural weathering of EAF (Electric Arc Furnace) and LF (Ladle Furnace) steel slag was evaluated through changes in the mineralogical and elemental composition. For that purpose, black steel slag and mixture of black and white steel slag were collected from two forest tracks, where they had been used as filler 19 and 35years ago respectively in a protected mountain area. Primary/original and secondary/degradation compounds were identified by spectroscopic techniques (Raman Spectroscopy, X-Ray Diffraction (XRD) and Scanning Electron Microscopy/Energy Dispersive X-Ray Spectroscopy (SEM/EDS)). Among secondary compounds, brucite (Mg(OH)2), portlandite (Ca(OH)2), thaumasite (Ca3Si(CO3)(SO4)(OH)6.12H2O) were identified. Secondary compounds indicated the reactivity of the slag with the surrounding environment (underground waters, atmosphere, lands and organisms), and volume change of the material. This effect could promote fractures in the road and thus, increase the possibility of leaching of hazardous elements (HE), present in the slags, to lands, rivers, etc. Besides, potentially toxic compounds such as hashemite (BaCrO4) and crocoite (PbCrO4) were identified as Cr(VI), which means a potential hazard to the surrounding environment and human life, since the sampling location is a mountain area with recreational activities. Cr(VI) can affect to the growth and development of plants, soil microbial communities, animals and cause allergy, asthma and respiratory tract cancer in humans. Moreover, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) allowed us to observe similar ranges of elemental concentrations in slag samples of the two forest tracks, with the exception of Ca, Mg, Sr, Pb, Ni and As concentration values. They were higher in the forest track with mixture of black and white slag than in the track with only black slag, and therefore, more likely to be leached and to be an environmental risk over time. By contrast, Na, V, Cr and W values were higher in the track with only black steel slag.

Migration of BTEX and phthalates from natural rubber latex balloons obtained from the Sri Lankan market.

The current study evaluates the migration of benzene, toluene, ethylbenzene, xylene (BTEX) and phthalates into artificial saliva from natural rubber latex (NRL) balloons available for sale in Sri Lanka. It was discovered that at least one BTEX compound migrated from almost all the brands. The migration of four phthalates; diethyl phthalate, dibutyl phthalate, di-isobutyl phthalate and butyl benzyl phthalate were also observed. Migratory levels of BTEX and phthalates in most of the balloon brands were above the permissible levels set by the European Union. Assessment of factors affecting the migratory levels indicated migration under active mouthing conditions and migration from the neck region of the balloons were significantly higher. The migratory levels were observed to decrease with storage time, and in certain brands the BTEX levels decreased below the permissible level. One-way ANOVA indicated no significant differences (p ≥ 0.05) in migratory levels of each individual compound within the same brand for both BTEX and phthalates. When compared among different brands, BTEX levels indicated significant differences (p ≤ 0.05), while phthalate levels were observed to not be significantly different (p ≥ 0.05). A significant difference was also observed (p ≤ 0.05) among the migratory levels of compounds under each test condition evaluated as factors affecting the migratory level. Furthermore, the solvent based colorants added to color the latex were found to be the source of BTEX and phthalates in the NRL balloons.

Human biomonitoring after chemical incidents and during short-term maintenance work as a tool for exposure analysis and assessment.

Human biomonitoring (HBM) is frequently used for the analysis and assessment of exposure to chemicals under routine working conditions. In recent years, HBM has also been applied to monitor the exposure of the general population, and of emergency responders in the aftermath of chemical incidents. Two examples of targeted HBM programs in the chemical industry are described and discussed in this paper: (1) analysis and assessment of the exposure of firefighters and chemical workers after the spill of p-chloroaniline from a burning chemical barrel, and (2) biomonitoring of maintenance workers potentially exposed to benzene during regular turnarounds. The results of these investigations underline that human biomonitoring contributes substantially to comprehensive exposure analyses, human health risk assessments and communication. In addition, regular HBM surveillance and feedback can assist in the continuous improvement of workplace safety measures and exposure control. In conclusion, data on accidental or short-term exposure to hazardous chemicals are an important source of information for the further development of limit and assessment values, the validation of biomarkers and of targeted HBM programs for both routine monitoring and disaster management.