Many of the products and drugs used commonly contain chemical components which may persist through sewage treatment works (STW) and eventually enter the aquatic environment as parent compounds, metabolites, or transformation products. Pharmaceuticals and personal care products (PPCPs) and other emerging contaminants (ECs) have been detected in waters (typically ng/L) as well as more recently bound to sediment and plastic particles (typically ng/g). Despite significant advancement of knowledge since the late 1990s, the fate of these contaminants/transformation products once introduced into the aquatic environment remains relatively unresolved. This review provides a unique focus on the fate of seven major groups of PPCPs/ECs in the aquatic environment, which is frequently not found in similar works which are often compound or topic-specific and limited in background knowledge. Key findings include: a) some replacements for regulation precluded/banned chemicals may be similarly persistent in the environment as those they replace, b) the adsorption of potentially bioactive chemicals to micro- and nanoplastics is a significant topic with risks to aquatic organisms potentially greater than previously thought, and c) micro-/nanoplastics are likely to remain of significant concern for centuries after regulatory limitations on their use become active due to the slow degradation of macro-plastics into smaller components. An interdisciplinary perspective on recent advances in the field is presented here in a unique way which highlights both the principle science and direction of research needed to elucidate the fate and transport patterns of aquatic PPCPs/ECs. Unlike similar reviews, which are often topic-specific, here we aim to present an overarching review of the field with focus on the occurrence, transformation and fate of emerging contaminants. Environmental presence of seven major classes of contaminants (analygesics, antibiotics, antineoplastics, beta-blockers, perfluorinated compounds, personal care products and plasticisers), factors affecting contaminant fate, association with plastic micro-/nanoparticles and photochemical transformation are comprehensively evaluated.

Pharmaceuticals and personal care products (PPCPs), other emerging contaminants (ECs), and metabolites thereof are ubiquitous in the environment, both built and natural. While such compounds have been environmentally present for some time, new pharmaceuticals and replacements for other ECs phased out due to regulatory limitations are continually being introduced to market. Non-target lower organisms are exposed through affected water, atmospheric emissions, precipitation, sediments, among other routes. Biological disruption/dysfunction (such as endocrine, developmental, and epigenetic disruption) has been reported in lower organisms exposed to trace levels of PPCPs and other ECs. Such disruption/dysfunction may not be exclusively present as traditional toxic response (e.g., cancer or death) but may only slightly alter natural biological processes as a result of exposure to an exogenous chemical (e.g., an increased heart rate or altered size of dorsal fat pads in fish). The epigenome and endocrine system appear to be relatively sensitive to many PPCPs/ECs, particularly during early development. Humans are exposed to ECs such as plasticizers and perfluorinated compounds (PFCs) mainly through ingestion (food and contaminated liquid) as well as interaction with day-to-day products (detergents, musk compounds in fragrances, etc.). Few, if any, studies have investigated trace-level toxicity of such ECs to humans as direct-exposure trials are highly unethical. However, numerous epidemiological links exist between the presence of contaminants in humans (blood, urine, and tissues) and the occurrence of diseases or other phenotypic alterations. Despite mounting interest and research, such trace-level effects on humans are greatly debated and often criticized. This paper reviews the current understanding of PPCP/EC toxicity. Discussion of general biological disruption/dysfunction of the following seven classes of PPCP/ECs is included: analgesics, antibiotics, antineoplastic compounds, beta-blockers, endocrine disrupting compounds, PFCs, and plasticizers. A review of receptor-mediated toxicity, non-monotonic dose response relationships, developmental toxicity, and environmental epigenetics is also included. Lastly, an overview of the proposed toxicity to humans is provided including discussion of significant criticism and direction of future research.

Organic contaminants such as pharmaceuticals, personal care products (PPCPs) and other emerging contaminants (ECs) are known to persist in the aquatic environment and many are indicated as endocrine, epigenetic, or other toxicants. Typically, the study of PPCPs/ECs in the aquatic environment is limited to their occurrence dissolved in river water. In this study, accumulation and spatial distribution of thirteen PPCPs/ECs were assessed in aquatic sediment (n = 23), periphyton (biofilm, n = 8), plants Callitriche sp. (n = 8) and Potamogeton sp. (n = 7) as well as amphipod crustaceans (Gammarus pulex, n = 10) and aquatic snails (Bithynia tentaculata, n = 9). All samples (n = 65) were collected from the Hogsmill, Blackwater and Bourne Rivers in southern England. Targeted PPCPs/ECs included pharmaceuticals, plasticisers, perfluorinated compounds, illicit drugs and metabolites. Extraction from solid matrices occurred using ultrasonic-assisted extraction followed by an in-house validated method for solid-phase extraction and subsequent liquid-chromatography tandem mass-spectrometry. Field-derived bioconcentration-factors and biota-sediment accumulation-factors were determined for all studied biota. Residues of studied contaminants were found in all sediment and biota. Concentrations of contaminants were generally higher in biota than sediment. Evidence suggests that the studied aquatic plants may effectively degrade bisphenol-A into its main transformation product hydroxyacetophenone, potentially mediated by cytochrome p450 and internalisation of contaminants into the cellular vacuole. A positive association between both hydrophobicity and PFC chain length and contaminant accumulation was observed in this work. Only PFCs, plasticisers and HAP were classified as either 'bioaccumulative' or 'very bioaccumulative' using BCF criteria established by guidelines of four governments. Contaminants appeared to be differentially bioaccumulative in biota, indicating there may be a need for a species-specific BCF/BSAF classification system. These data form a detailed accounting of PPCP/EC fate and distribution in the aquatic environment highlighting accumulation at lower trophic levels, a potential source for higher organisms.

Background: Recently, the accuracies of many commercially available immunoassays for Vitamin D have been questioned. Liquid chromatography tandem mass spectrometry (LC- MS/MS) has been shown to facilitate accurate separation and quantification of the major circulating metabolite 25-hydroxyvitamin-D3 (25OHD3) and 25-hydroxyvitamin-D2 (25OHD2) collectively termed as 25OHD. However, among other interferents, this method may be compromised by overlapping peaks and identical masses of epimers and isobars, resulting in inaccuracies in circulating 25OHD measurements. The aim of this study was to develop a novel LC-MS/MS method that can accurately identify and quantitate 25OHD3 and 25OHD2 through chromatographic separation of 25OHD from its epimers and isobars. Methods: A positive ion electrospray ionisation (ESI) LC-MS/MS method was used in the Multiple Reaction Monitoring (MRM) mode for quantification. It involved i) liquid-liquid extraction, ii) tandem columns (a high resolution ZORBAX C18 coupled to an ULTRON chiral, with guard column and inlet filter), iii) Stanozolol-D3 as internal standard, and iv) identification via ESI and monitoring of three fragmentation transitions. To demonstrate the practical usefulness of our method, blood samples were collected from 5 healthy male Caucasian volunteers; age range 22 to 37 years and 25OHD2, 25OHD3 along with co-eluting epimers and analogues were quantified. Results: The new method allowed chromatographic separation and quantification of 25OHD2, 25OHD3, along with 25OHD3 epimer 3-epi-25OHD3 and isobars 1-α-hydroxyvitamin-D3 (1αOHD3), and 7-α-hydroxy-4-cholesten-3-one (7αC4). The new assay was capable of detecting 0.25 ng/mL of all analytes in serum. Conclusions: To our knowledge, this is the first specific, reliable, reproducible and robust LC-MS/MS method developed for the accurate detection of 25OHD (Vitamin D). The method is capable of detecting low levels of 25OHD3 and 25OHD2 together with chromatographic separation from the co-eluting epimers and isobars and circumvents other instrumental/analytical interferences. This analytical method does not require time-consuming derivatisation and complex extraction techniques and could prove very useful in clinical studies.