Pharmaceuticals in biota in the aquatic environment: analytical methods and environmental implications

The presence of pharmaceuticals in the aquatic environment is an ever-increasing issue of concern as they are specifically designed to target specific metabolic and molecular pathways in organisms, and they may have the potential for unintended effects on nontarget species. Information on the presence of pharmaceuticals in biota is still scarce, but the scientific literature on the subject has established the possibility of bioaccumulation in exposed aquatic organisms through other environmental compartments. However, few studies have correlated both bioaccumulation of pharmaceutical compounds and the consequent effects. Analytical methodology to detect pharmaceuticals at trace quantities in biota has advanced significantly in the last few years. Nonetheless, there are still unresolved analytical challenges associated with the complexity of biological matrices, which require exhaustive extraction and purification steps, and highly sensitive and selective detection techniques. This review presents the trends in the analysis of pharmaceuticals in aquatic organisms in the last decade, recent data about the occurrence of these compounds in natural biota, and the environmental implications that chronic exposure could have on aquatic wildlife.     

Liquid chromatography methodologies for the determination of steroid hormones in aquatic environmental systems

Steroid hormones are a diverse group of natural and synthetic compounds. Their wide use in human and veterinary medicine results in their continual introduction into the environment. In recent years, environmental concern over steroids that act as endocrine disruptors has increased because of their adverse effects on organisms or their progeny. Moreover, as these compounds are not totally removed from sewage in wastewater treatment plants, they can reach the aquatic environment and persist due to their physicochemical characteristics.For this reason, a major trend in analytical chemistry is the development of rapid and efficient procedures for the extraction, determination and quantification of steroid hormones in environmental samples. Over the past few decades, the significant expansion of liquid chromatography technology utilizing mass spectrometry detection has led to applications with increased selectivity and sensitivity. Optimized extraction and microextraction techniques combined to these liquid chromatography techniques have lowered detection and quantification limits to the ng L⁻¹–μg L⁻¹ range, which is the concentration of steroid hormones in liquid, solid and biota samples.In this paper, the state-of-the-art techniques for the analysis of steroid hormones focused mainly in based liquid chromatography methods in liquid and aquatic solid and biota samples are reviewed. Handling, storage, extraction and detection methodologies are reviewed and compared for all families of steroid hormones.     

Sulphonamide Residues in Italian Surface and Drinking Waters: A Small Scale Reconnaissance

The occurrence of antibiotics in the aquatic environment is an important emerging issue due to potential adverse effect of these compounds on ecosystem and human health. For a correct environmental risk assessment there is a need for appropriate analytical methods for monitoring antibiotic residues in a variety of water matrices. This paper describes a method for the determination of eleven sulphonamide compounds in surface and drinking waters using solid-phase extraction and liquid chromatography-tandem mass spectrometry. Recoveries of the analytes in both surface and drinking water matrices at different fortification levels, always exceed 87%; the limits of quantification in surface water samples are between 0.005 and 0.021 μg L⁻¹ depending on the compound, and the interday method precision is less than 12%. Matrix effects were evaluated in drinking and surface water samples. The method has been applied to a small scale reconnaissance of river, lake, mineral and municipal water samples; results indicate the occurrence of sulphonamides in some surface and mineral waters analyzed.     

Determination of fifteen priority phenolic compounds in environmental samples from Andalusia (Spain) by liquid chromatography–mass spectrometry

This work describes the optimisation of a method to determinate fifteen phenolic compounds in waters, sediments and biota (green marine algae) by liquid chromatography coupled to mass spectrometry (LC-MS) with atmospheric pressure chemical ionisation (APCI) in the negative mode. The LC separations of the studied compounds and their MS parameters were optimised in order to improve selectivity and sensitivity. Separation was carried out with a C₁₈ column using methanol and 0.005% acid acetic as mobile phase in gradient mode. The molecular ion was selected for the quantitation in selective ion monitoring (SIM) mode. A solid-phase extraction (SPE) method was applied in order to preconcentrate the target analytes from water samples. However, extraction of the compounds from sediment and biota samples was carried out by liquid–solid extraction with methanol/water after studying the influence of other organic solvents. In addition, a clean-up step by SPE with HLB Oasis cartridges was necessary for sediments and biota. The proposed analytical methodology was validated in the target environmental matrices by the analysis of spiked blank matrix samples. Detection limits were 10–50 ng L^–1 for water, 1–5 g kg^–1 for sediments and 2.5–5 g kg^–1 for biota samples. Good recoveries and precision values were obtained for all matrices. This methodology has been successfully applied to the analysis of incurred water, sediment and biota samples from Andalusia (Spain).     

Determination of perfluorinated compounds in aquatic organisms: a review

Bioaccumulation of PFAS in aquatic organisms is an environmental problem of growing concern around the world. This problem has been tackled by regulatory bodies by proposing EQS for biota in EU water bodies and tolerable daily intake for food. The introduction of regulatory limits requires the availability of harmonised and validated analytical methods of sufficient sensitivity. This paper reviews recent advances in analytical methods for analysis of PFAS in aquatic organisms. The methods available for biota analysis are mostly based on three extraction procedures: ion-pair extraction, solvent liquid extraction, and alkaline digestion. The resulting extracts are then subjected to different clean-up or enrichment steps on solid adsorbents, for example graphitized carbon black, C₁₈, and WAX phases. All methods reviewed in this work give reliable results but are partially validated only, because of the lack of certified reference materials and regular interlaboratory exercises. The few interlaboratory exercises performed on real unspiked samples did not afford satisfactory results for PFAS other than PFOS, especially for matrices with high lipid content, for example mussels. The reasons for those partially negative results have been identified, and can mainly be attributed to calibration procedures and availability and purity of standards. The urgent need for certified reference materials for this type of analysis is emphasized.     

Analytical methods for antifouling booster biocides determination in environmental matrices: A review

Since the discovery of their toxicity to aquatic environments, antifouling booster biocides (ABBs) have been widely researched and detected at trace levels in diverse environmental compartments including water, sediment, and, less frequently, biota. Hence, the reliable assessment of environmental risks posed by ABBs requires the development of analytical methods sufficiently robust, accurate, and precise for the simultaneous trace-level determination of ABBs. Herein, we summarize outstanding sample preparation procedures for the analysis of main ABBs in environmental matrices, describing techniques ranging from traditional extraction methods to novel miniaturized and micro-extraction ones, which have recently received much attention due to their reduced number of steps, low operational cost, and greater respect for the environment. The main applied chromatographic-based methods coupled to different detection techniques are also addressed. Despite the recent development of numerous ABBs determination methods, this topic continues to draw attention because of the lack of standardization among methods, despite legislation set up maximum standards levels for selected ABBs, and the need to monitor ABB transformation products for a reliable ecological risk assessment.     

加速溶剂萃取-分子筛固相萃取-气相色谱-串联质谱法测定土壤中多氯萘北大核心CSCD

新污染物引发的环境和健康风险正逐步受到社会各界的广泛关注,我国第十四个五年规划和2035年远景目标纲要明确“重视新污染物治理”。作为新型的持久性有机污染物,多氯萘(PCNs)在土壤中通常处于痕量水平,一般需要经过多层硅胶柱/氧化铝柱等复杂的净化方法,再结合有效的分析手段才能实现准确测定。关注土壤中多氯萘分离分析方法可以为掌握和监管其在土壤中的污染状况提供技术和方法支持。研究以13X分子筛作为固相萃取吸附剂,评价了其对多氯萘的净化效果。研究发现:使用正己烷作为上样溶剂和淋洗剂,10 mL二氯甲烷/正己烷(2∶15,v/v)为洗脱溶剂,可以实现PCNs与脂类大分子等干扰物的选择性分离,且多氯萘内标的平均回收率为56.1%~88.0%。与凝胶渗透色谱法、弗罗里硅土固相萃取柱以及多层硅胶柱/氧化铝柱相比,13X分子筛对土壤提取液的净化效果优于前两种净化方法,可以获得与多层硅胶/氧化铝柱相近的净化效果(53.0%~117.0%),而且操作更加简单,环境更加友好,分析成本大幅度下降。在此基础之上,建立了加速溶剂萃取-分子筛固相萃取,结合气相色谱-三重四极杆质谱法测定土壤中PCNs的分析方法。PCNs同族体的方法检出限为0.009~0.6 ng/g。采用基质加标法评价了本方法的精密度和准确度,CN-3、13、42、46、52、53、73、75在低、中、高加标水平下的平均加标回收率分别为70%~128%、71%~115%和61%~114%,测定结果的相对标准偏差分别为4.2%~23%、6.5%~31%和4.7%~22%,满足痕量分析的要求且平行性较好。从整个分析流程来看,13X分子筛有望成为新污染物净化的新型固相萃取吸附剂,并在土壤新污染物普查中发挥重要作用。     

Analytical methods for the determination of persistent ingredients of personal care products in environmental matrices

Concern about the environmental fate and potential effects of synthetic organic chemicals used in soaps, lotions, toothpaste, and other personal care products continues to increase. This review describes procedures used for the analysis of five classes of these compounds–synthetic musk fragrances, antimicrobials, ultraviolet filters, insect repellents, and parabens–in water, sediment, sewage sludge, air, and aquatic biota. The primary focus is on sample extraction and preparation methods for these compounds. Instrumental methods commonly used for these compounds are also discussed. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Dechlorane Plus and related compounds in aquatic and terrestrial biota: a review

Dechlorane Plus, dechlorane 602, dechlorane 603 and dechlorane 604 are flame retardants that have been used for a long time as a substitute for mirex, but they have not been noticed as environmental contaminants until recently (2006). Regardless of their large molecular size and very high lipophilicity (log K _OW?>?9), Dechlorane Plus and related compounds have been detected in different aquatic and terrestrial species, supporting their bioaccumulation and biomagnification. Moreover, some studies showed different behaviour of the syn-Dechlorane Plus and anti-Dechlorane Plus isomers in the environment and different biomagnification factors in biota. This review describes the different analytical approaches applied to the determination of Dechlorane Plus and related compounds. Moreover, a summary of their levels in aquatic and terrestrial biota, as well as in humans, is presented, showing also current research results on their bioaccumulation and biomagnification potential. Finally, isomer-specific bioaccumulation of Dechlorane Plus is also discussed.     

Determination of pesticide transformation products: A review of extraction and detection methods

Pesticides are widely applied and they can produce a variety of transformation products (TPs), through different pathways and mechanisms. Nowadays there is a growing interest related to the determination of pesticide TPs in several matrices (environmental, food and biological samples), due to these compounds can be more toxic and persistent than parent compounds, and some of them can be used as markers of exposure to different pesticides. Although solid-phase extraction (SPE) is mainly used for the extraction of TPs, alternative techniques such as solid-phase microextraction (SPME) and liquid-phase extraction (LPE) can be used. These TPs are mainly determined by liquid chromatography (LC) due to the recent developments in this technique, especially when it is coupled to mass spectrometry (MS) detectors, allowing the determination of known and/or unknown TPs. Furthermore, MS is a very valuable tool for the structural elucidation of unknown TPs. This review discusses all phases of analytical procedure, including sample treatment and analysis, indicating the main problems related to the extraction of TPs from several matrices due to their high polarity, as well as the different alternatives found for the simultaneous determination of parent compounds and TPs, using chromatographic techniques coupled to MS detection.     

Prediction Helps Analytical Experimental Work for Environmental Purposes

 Analytical work, especially for environmental purposes, involves in the typical case determination of organic compounds in compartments, where their presence is very small. Identification of the appropriate experimental technique, whose range of applicability covers the concentration value involved, requires an estimate of this value. To this purpose, we present in this study a methodology for the prediction of the concentration of organic pollutants in the various environmental compartments (aquatic biota, air, sediment and soil) from the knowledge of the concentration in one of them. In case where the pollutant’s concentration is not available for any of the compartments, the proposed methodology can be used to estimate the maximum expected concentration in each one of them assuming that the water phase is saturated with the pollutant. The latter value can be obtained from a simple correlation presented here. The methodology is based on the correlation of the partition coefficients of pollutants among the various environmental compartments with two important thermodynamic quantities of pollutants: the octanol/water partition coefficient and the Henry’s law coefficient, which can be easily predicted by simple models presented here. Application of the methodology to field experimental data gives very satisfactory results at least for identifying the appropriate experimental technique.     

Pharmaceutical residues in environmental waters and wastewater: current state of knowledge and future research

Pollution from pharmaceuticals in the aquatic environment is now recognized as an environmental concern in many countries. This has led to the creation of an extensive area of research, including among others: their chemical identification and quantification; elucidation of transformation pathways when present in wastewater-treatment plants or in environmental matrices; assessment of their potential biological effects; and development and application of advanced treatment processes for their removal and/or mineralization. Pharmaceuticals are a unique category of pollutants, because of their special characteristics, and their behavior and fate cannot be simulated with other chemical organic contaminants. Over the last decade the scientific community has embraced research in this specific field and the outcome has been immense. This was facilitated by advances in chromatographic techniques and relevant biological assays. Despite this, a number of unanswered questions exist and still there is much room for development and work towards a more solid understanding of the actual consequences of the release of pharmaceuticals in the environment. This review tries to present part of the knowledge that is currently available with regard to the occurrence of pharmaceutical residues in aquatic matrices, the progress made during the last several years on identification of such compounds down to trace levels, and of new, previously unidentified, pharmaceuticals such as illicit drugs, metabolites, and photo-products. It also tries to discuss the main recent findings in respect of the capacity of various treatment technologies to remove these contaminants and to highlight some of the adverse effects that may be related to their ubiquitous existence. Finally, socioeconomic measures that may be able to hinder the introduction of such compounds into the environment are briefly discussed.     

Methods for the extraction of microplastics in complex solid,water and biota samples

The widespread distribution of plastics, their persistence and ability to act as a vector of toxic chemicals has rendered them concerning emergent pollutants. The quantification of these contaminants is highly relevant for the evaluation of anthropogenic impacts on aquatic and terrestrial ecosystems and dependent of the efficacy of methods to separate microplastics from environmental matrices. Little information is available about the microplastic extraction methods on complex samples – i.e. samples with multiple types of matrices. Herein, methods for the separation of microplastics from complex samples are summarized and discussed based on their advantages and drawbacks focused on a comparative analysis of their efficiency on organic matter removal, polymer recovery and preservation of plastic integrity. The efficiency on microplastic recovery and organic matter reduction, as well as the examination of the effects of treatments on plastics are closely linked to the density and digestion approaches selected, the polymer features and the environmental matrix analyzed. High-density salt solutions are more effective for density separation, while oxidative methods have recurrently shown better rates of organic matter reduction (particularly in vegetal-rich samples) and plastic recovery, with little impact on plastics, while 10 % KOH has been described as highly efficient in samples containing animal organic matter. This comparative analysis highlights the benefits and limitations of different approaches for the analysis of microplastics in complex samples which may be helpful for the optimization and harmonization of the methods.     

Organic UV filters in marine environments: An update of analytical methodologies,occurrence and distribution

Ultraviolet filters (UV Filters) are compounds that are widely employed in personal care products such as sunscreens to protect the skin from sun damage, but they are also added to other products, such as food packaging, plastics, paints, textiles, detergents, etc. The continuous use of these products causes the release of a substantial amount of these products into the marine environment through direct input or wastewater discharge, and thus they are becoming an important class of contaminants of emerging concern. A correlation between their occurrence and different negative effects on marine biota has been reported.Taking into account all the possible impacts on the environment, knowledge of their presence and distribution in the different compartments of the ecosystems, ranging from waters and sediments to aquatic organisms, which potentially suffer from bioaccumulation and biomagnification processes, is essential. High concentrations of ultraviolet filters have been found in samples collected from across the entire planet, even in polar regions, revealing their global distribution.Therefore, interest in the sensitive determination of ultraviolet filters in several marine matrices has increased. In this article, an overall review of the more recently reported analytical chemistry methods for identifying and quantifying these compounds in marine environmental samples is presented. We compare and discuss the potential advantages and disadvantages of every step involved in the analytical procedure, including the pre-treatment, treatment and extraction processes that are required to avoid matrix effects. Moreover, we describe the worldwide occurrence and distribution of those most important UV filters.     

Analysis of organic compounds in environmental samples by headspace solid phase microextraction

The analysis of samples contaminated by organic compounds is an important aspect of environmental monitoring. Because of the complex nature of these samples, isolating target organic compounds from their matrices is a major challenge. A new isolation technique, solid phase microextraction, or SPME, has recently been developed in our laboratory. This technique combines the extraction and concentration processes into one step; a fused silica fiber coated with a polymer is used to extract analytes and transfer them into a GC injector for thermal desorption and analysis. It is simple, rapid, inexpensive, completely solvent-free, and easily automated. To minimize matrix interferences in environmental samples, SPME can be used to extract analytes from the headspace above the sample. The combination of headspace sampling with SPME separates volatile and semi-volatile analytes from non-volatile compounds, thus greatly reducing the interferences from non-target compounds. This paper reports the use of headspace SPME to isolate volatile organic compounds from various matrices such as water, sand, clay, and sludge. By use of the technique, benzene, toluene, ethyl-benzene, and xylene isomers (commonly known as BTEX), and volatile chlorinated compounds can be efficiently isolated from various matrices with good precision and low limits of detection. This study has found that the sensitivity of the method can be greatly improved by the addition of salt to water samples, water to soil samples, or by heating. Headspace SPME can also be used to sample semi-volatile compounds, such as PAHs, from complex matrices.     

Potential effects of climate change on the chemical quality of aquatic biota

Climate changes can alter and modify the distribution and the partitioning of contaminants in water bodies through several factors (e.g., rise in temperature, decrease in oxygen through water scarcity, acidification and remobilization of pollutants in sediments due to flooding). Other indirect effects can be linked to climate changes (e.g., increased use of pesticides due to the rise of plant diseases caused by new vectors and erosion of coastal areas due to rise in sea level). All these factors have the potential to enhance the bioavailability of dangerous pollutants with bioaccumulative properties with an increasing risk of transfer in the food chain.The data available on aquatic species for compounds such as, polychlorinated biphenyls, dioxins and mercury show that the legislative standards for food are exceeded in some areas. These data also show that levels in aquatic biota of other emerging compounds with bioaccumulative properties (such as, perfluorinated octane sulfonate, polybrominated diphenyl ethers and hexabromocyclododecane can be relevant in some areas and at some trophic levels. In particular, the effect of climate changes can be relevant in vulnerable water bodies (e.g., estuaries of rivers or coastal lagoons), where fishing, extensive and intensive aquaculture activities and sites of high biodiversity value are often present.For these reasons, there is a need to change the water-monitoring strategies with a focus on analytical methods for biota determination and to have monitoring programs that include detection of long-term trends and share procedures for the setting of quality criteria for biota.     

Mass spectrometry for identifying pharmaceutical biotransformation products in the environment

Many classes of pharmaceuticals have been detected in wastewaters and surface waters around Europe, but little is known about their occurrence, fate and potential harmful effects on the environment, and that makes them an important group among those compounds considered to be new emerging contaminants. To understand the cycling of pharmaceuticals and their metabolites, it is essential to possess qualitative and quantitative information on their presence in the environment. This review covers the current status and future prospects of advanced hyphenated mass spectrometric (MS) techniques (gas chromatography-MS (GC-MS) and liquid chromatography-MS (LC-MS)) in elucidating the structures of trace contaminants, namely pharmaceutical biodegradation products in complex environmental matrices. The article is oriented towards technique and method and discusses capabilities, potential and limitations of different GC and LC mass analyzers (quadrupole, ion trap, time-of-flight and hybrid techniques) in dealing with analytical challenges of complex matrices and trace contaminants. We also give practical examples of their applications. The main scope of this article is to support and to facilitate the on-going research on pharmaceutical biodegradation products in environmental samples.     

水产品中有害物质分析样品前处理技术研究进展

水产品含有丰富的蛋白、维生素和多种微量元素,是人们摄取动物性蛋白质的重要来源之一,我国是世界上最大的水产品消费国,其质量安全问题一直备受关注。但水产样品基质复杂,有害物质的含量低,须对其进行分离富集后才能进行检测,传统的液-液萃取、固相萃取和快速固相分散萃取等样品前处理技术在水产品分析中得到广泛应用,同时针对一些挥发性和超痕量有害物质检测时,固相微萃取同样体现出巨大优势。这些样品前处理技术可以有效去除基体对分析对象的干扰,提高检测方法的灵敏度和准确度。根据目标分析物性质的不同,选择合适的样品前处理技术,是水产品中有害物质分析的关键步骤。该文以水产品中有害物的来源不同,将其分为3类:(1)水产品中环境污染物的分析;(2)养殖运输和加工过程中有害物的分析;(3)水产品中生物毒素的分析。以这3类有害物质的分析为主线,综述了近10年水产品中有害物质分析的样品前处理技术,包括液-液萃取、固相萃取、固相微萃取、快速固相分散萃取和磁性固相萃取等。此外,还对各种技术的优缺点进行了探讨,并对其未来发展方向进行了展望。     

Simply Applicable Method for Microplastics Determination in Environmental Samples

Microplastics (MPs) have gained significant attention in the last two decades and have been widely researched in the marine environment. There are, however, less studies on their presence, routes of entry, and impacts on the biota in the soil environment. One of the main issues in the study of MPs is a lack of standardized methods for their identification in environmental samples. Currently the most commonly used techniques are thermal desorption gas chromatography–mass spectrometry (GC–MS) methods and pyrolysis followed by GC–MS. In this study, headspace-solid phase microextraction followed by GC–MS is proposed as a simple and widely applicable method for the determination of commonly present polymer MPs (polyethylene terephthalate, polystyrene, polyvinyl chloride, polyethylene, and polypropylene) in environmental samples, for analytical laboratories with basic equipment worldwide. The proposed method is based on the identification of compounds, which are formed during the well-controlled melting process of specific coarse (1–5 mm) and fine fraction (1 mm–100 μm) MPs. The method was upgraded for the identification of individual polymer type in blends and in complex environmental matrices (soil and algae biomass). The successful application of the method in complex matrices makes it especially suitable for widescale use.     

Molecularly imprinted solid‐phase extraction coupled with ultra high performance liquid chromatography and fluorescence detection for the determination of estrogens and their metabolites in wastewater

Estrogens are an important class of endocrine‐disrupting compounds, and their contamination of environmental waters through the effluents of wastewater treatment plants could have an important impact on aquatic biota, even at low concentrations. For this reason, the development of selective and sensitive extraction methodologies, which permit the identification and quantification of these compounds at trace level concentrations, is very important. In this study, a quantitative method based on molecularly imprinted solid phase extraction coupled to ultra high performance liquid chromatography with fluorescence detection has been developed. It has been used for the simultaneous determination of three estrogens and two of their metabolites in water samples from wastewater treatment plants. The method developed presents satisfactory limits of detection (between 0.18 and 0.45 ng·mL^?1), good recoveries (higher than 60%) and low relative standard deviations (under 10%). The method was used to analyze wastewater from a veterinary hospital as well as influent and effluent samples of a wastewater treatment plant of Gran Canaria (Spain) The concentrations of the detected hormones ranged from 1.35 to 2.57 ng·mL^?1.