Analysis of emerging and related pollutants in aquatic biota

Water bodies cover approximately 70 % of the earth´s surface, making them ecosystems with a high environmental value and the habitat for numerous species of flora and fauna. Emerging pollutants (EPs) are ubiquitous anthropogenic compounds of environmental concern that can be found at different concentration levels in matrices such as sediment, water and aquatic biota. In addition, EPs can be bioaccumulated and biomagnified, inducing adverse effects on biota, and posing a risk to humans when contaminated biota is consumed. Unlike abiotic matrices, the occurrence of EPs in aquatic biota has not been widely studied. This is probably because their complexity, due to the presence of lipids, proteins and other organic compounds, makes the extraction and analysis of EPs difficult. This review gathers the most relevant analytical methods published between 2014 and 2019, comparing them and evaluating their strengths and weaknesses. It is intended to provide a better understanding of the development of new and improved methods, and to be a reference for researchers who are looking for the best methodology for their studies.     

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.     

An overview of UV-absorbing compounds (organic UV filters) in aquatic biota

The purpose of this article is to summarize biological monitoring information on UV-absorbing compounds, commonly referred as organic UV filters or sunscreen agents, in aquatic ecosystems. To date a limited range of species (macroinvertebrates, fish, and birds), habitats (lakes, rivers, and sea), and compounds (benzophenones and camphors) have been investigated. As a consequence there is not enough data enabling reliable understanding of the global distribution and effect of UV filters on ecosystems. Both liquid chromatography and gas chromatography coupled with mass spectrometry-based methods have been developed and applied to the trace analysis of these pollutants in biota, enabling the required selectivity and sensitivity. As expected, the most lipophilic compounds occur most frequently with concentrations up to 7112?ng?g^?1 lipids in mussels and 3100?ng?g^?1 lipids (homosalate) in fish. High concentrations have also been reported for 4-methylbenzilidenecamphor (up to 1800?ng?g^?1 lipids) and octocrylene (2400?ng?g^?1 lipids). Many fewer studies have evaluated the potential bioaccumulation and biomagnification of these compounds in both fresh and marine water and terrestrial food webs. Estimated biomagnification factors suggest biomagnification in predator–prey pairs, for example bird–fish and fish–invertebrates. Ecotoxicological data and preliminary environmental assessment of the risk of UV filters are also included and discussed.     

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.     

Atmospheric levels and distribution of Dechlorane Plus in an E-waste dismantling region of East China

Atmospheric concentrations of Dechlorane Plus(DP)were investigated in Taizhou,an electronic-waste(E-waste)dismantling region in East China.Passive air samplers with polyurethane foam(PUF)disks were deployed every three months during the sampling period of September 2009-August 2010.The total DP(syn-and anti-DP)concentrations in air ranged from not detected to 277 pg/m~3,with a mean concentration of 53.9 pg/m~3.A generally declining trend of DP levels was found from the E-waste dismantling region to the peripheral areas.The median values of total DP concentrations in autumn,winter,spring and summer were 52.2,28.8,39.7 and 30.1 pg/m~3,respectively.The seasonal variations of DP concentrations were mainly associated with the intensity of E-waste dismantling activities and meteorological conditions.The mean value of anti-DP fractional abundance(f_(anti))was 0.74±0.08,which was consistent with those in the commercial DP products.This study confirmed a significant emission source related to the distribution of atmospheric DP in the E-waste dismantling area and supplied information for the seasonal variation of DP in the atmosphere.     

Comparison of Dechlorane Plus Concentrations in Sequential Blood Samples of Pregnant Women in Taizhou,China

To develop an appropriate sampling strategy to assess the intrauterine exposure to dechlorane plus (DP), we investigated DP levels in sequential maternal blood samples collected in three trimesters of pregnancy, respectively, from women living in Taizhou. The median concentration of DPs (sum of syn-DP and anti-DP) in all samples was 30.5 pg g⁻¹ wet-weight and 5.01 ng g⁻¹ lipid-adjusted weight, respectively. The trimester-related DP concentrations were consistently strongly correlated (p < 0.01), indicating that a single measurement of DP levels could represent intrauterine exposure without sampling from the same female repeatedly; however, the wet-weight levels significantly increased across trimesters (p < 0.05), while the lipid-adjusted levels did not significantly vary. Notably, whether lipid-adjusted weight or wet-weight levels, the variation extent of DP across trimesters was found to be less than 41%, and those for other persistent organic pollutants (POPs) reported in the literature were also limited to 100%. The limitation in variation extents indicated that, regardless of the time of blood collection during pregnancy and how the levels were expressed, a single measurement could be extended to screen for exposure risk if necessary. Our study provides different strategies for sampling the maternal blood to serve the requirement for assessment of in utero exposure to DP.     

Automated sample preparation-fractionation for the measurement of dioxins and related compounds in biological matrices: a review

This article reviews some of the recent developments in the extraction and clean-up areas of biological samples dedicated to dioxin and related compound analysis. A brief introduction on the major dioxin contamination events, which have occurred in the food chain, is given to illustrate the need of fast high throughput methods in case of crises. The emphasis of this paper is the method development based upon reliable instrumental extraction techniques for rapid sample processing and automation such as; supercritical fluid extraction (SFE), microwave-assisted extraction (MAE), pressurized liquid extraction (PLE) and, solid-phase extraction (SPE). The PLE and SPE are also discussed in conjunction with the use of a multi-column automated clean-up system that can accommodate up to 5 g of extracted lipids. The fractionation in sub-groups of analytes during the clean-up process allows the isolation of various types of toxicants from a single sample and illustrates the versatility of the system. An integrated extraction and clean-up instrument is finally presented in terms of feasibility and attainable sample turnover for the parallel processing of liquid and solid biological samples.     

The role of UV-B radiation in aquatic and terrestrial ecosystems--an experimental and functional analysis of the evolution of UV-absorbing compounds

We analysed and compared the functioning of UV-B screening pigments in plants from marine, fresh water and terrestrial ecosystems, along the evolutionary line of cyanobacteria, unicellular algae, primitive multicellular algae, charophycean algae, lichens, mosses and higher plants, including amphibious macrophytes. Lichens were also included in the study. We were interested in the following key aspects: (a) does the water column function effectively as an 'external UV-B filter'?; (b) do aquatic plants need less 'internal UV-B screening' than terrestrial plants?; (c) what role does UV screening play in protecting the various plant groups from UV-B damage, such as the formation of thymine dimers?; and (d) since early land 'plants' (such as the predecessors of present-day cyanobacteria, lichens and mosses) experienced higher UV-B fluxes than higher plants, which evolved later, are primitive aquatic and land organisms (cyanobacteria, algae, lichens, mosses) better adapted to present-day levels of UV-B than higher plants? Furthermore, polychromatic action spectra for the induction of UV screening pigments of aquatic organisms have been determined. This is relevant for translating 'physical' radiation measurements of solar UV-B into 'biological' and 'ecological' effects. From the action spectra, radiation amplification factors (RAFs) have been calculated. These action spectra allow us to determine any mitigating or antagonistic effects in the ecosystems and therefore qualify the damage prediction for the ecosystems under study. We summarize and discuss the main results based on three years of research of four European research groups. The central theme of the work was the investigation of the effectiveness of the various screening compounds from the different species studied in order to gain some perspective of the evolutionary adaptations from lower to higher plant forms. The induction of mycosporine-like amino acids (MAAs) was studied in the marine dinoflagellate Gyrodinium dorsum, the green algal species Prasiola stipitata and in the cyanobacterium Anabaena sp. While visible (400-700 nm) and long wavelength UV-A (315-400 nm) showed only a slight effect, MAAs were effectively induced by UV-B (280-315 nm). The growth of the lower land organisms studied, i.e. the lichens Cladina portentosa, Cladina foliacaea and Cladonia arbuscula, and the club moss Lycopodiumannotinum, was not significantly reduced when grown under elevated UV-B radiation (simulating 15% ozone depletion). The growth in length of the moss Tortula ruralis was reduced under elevated UV-B. Of the aquatic plants investigated the charophytes Chara aspera showed decreased longitudinal growth under elevated UV-B. In the 'aquatic higher plants' studied, Ceratophyllum demersum, Batrachium trichophyllum and Potamogeton alpinus, there was no such depressed growth with enhanced UV-B. In Chara aspera, neither MAAs nor flavonoids could be detected. Of the terrestrial higher plants studied, Fagopyrum esculentum, Deschampsia antarctica, Vicia faba, Calamagrostis epigejos and Carex arenaria, the growth of the first species was depressed with enhanced UV-B, in the second species length growth was decreased, but the shoot number was increased, and in the latter two species of a dune grassland there was no reduced growth with enhanced UV-B. In the dune grassland species studied outdoors, at least five different flavonoids appeared in shoot tissue. Some of the flavonoids in the monocot species, which were identified and quantified with HPLC, included orientin, luteolin, tricin and apigenin. A greenhouse study with Vicia faba showed that two flavonoids (aglycones) respond particularly to enhanced UV-B. Of these, quercetin is UV-B inducible and mainly located in epidermal cells, while kaempferol occurs constitutively. In addition to its UV-screening function, quercetin may also act as an antioxidant. Polychromatic action spectra were determined for induction of the UV-absorbing pigments in three photosynthetic organisms, representing very different taxonomic groups and different habitats. In ultraviolet photobiology, action spectra mainly serve two purposes: (1) identification of the molecular species involved in light absorption; and (2) calculation of radiation amplification factors for assessing the effect of ozone depletion. Radiation amplification factors (RAFs) were calculated from the action spectra. In a somewhat simplified way, RAF can be defined as the percent increase of radiation damage for a 1% depletion of the ozone layer. Central European summer conditions were used in the calculations, but it has been shown that RAF values are not critically dependent on latitude or season. If only the ultraviolet spectral region is considered, the RAF values obtained are 0.7 for the green alga Prasiola stipitata, 0.4 for the dinoflagellate Gyrodinium dorsum, and 1.0 for the cyanobacterium Anabaena sp. In the case of P. stipitata, however, the effect of visible light (PAR, photosynthetically active radiation, 400-700 nm) is sufficient to lower the RAF to about 0.4, while the PAR effect for G. dorsum is negligible. RAFs for some damage processes, such as for DNA damage (RAF=2.1 if protective effects or photorepair are not considered [1]), are higher than those above. Our interpretation of this is that if the ozone layer is depleted, increased damaging radiation could overrule increased synthesis of protective pigments. In addition to investigating the functional effectiveness of the different screening compounds, direct UV effects on a number of key processes were also studied in order to gain further insight into the ability of the organisms to withstand enhanced UV-B radiation. To this end, the temperature-dependent repair of cyclobutane dimers (CPD) and (6-4) photoproducts induced by enhanced UV-B was studied in Nicotiana tabacum, and the UV-B induction of CPD was studied in the lichen Cladonia arbuscula. Also, photosynthesis and motility were monitored and the response related to the potential function of the screening compounds of the specific organism.     

Ionic alkylleads in avian tissues from aquatic and terrestrial environments

Ionic alkyllead concentrations in soft tissues of pigeons from urban Montreal and environs were appreciably different from the variety and concentrations of alkyllead analytes which characterized mallard ducks culled from a sanctuary in eastern Ontario. The major toxicant in pigeons, triethyllead (Et₃Pb⁺) reflected the exclusive use of tetraethyllead as a gasoline additive in both regions. Urban colonies of pigeons were characterized by significantly greater concentrations of Et₃Pb⁺ than were specimens from a suburban/rural colony. In contrast, the major toxicant in ducks was trimethyllead although six other alkyllead analytes were also observed. An environmentally mediated methylation of Pb²⁺ which is more active in (but not restricted to) aquatic environments is postulated to account for the ubiquity of trimethyllead in ducks.     

气相色谱-质谱法检测人血清样品中新型含氯阻燃剂德克隆

采用液液萃取,气相色谱-负离子化学电离质谱技术,建立了人体血清样品中新型含氯阻燃剂德克隆(DP)的分离分析方法.血清样品蛋白质变性后,采用液液萃取法提取脂肪,再采用浓H2SO4破坏法去除大部分脂肪,最后采用酸性硅胶柱进一步净化.净化后的样品经浓缩富集,采用气相色谱-负离子化学电离质谱仪测定样品中DP两种同分异构体的含量...     

2, 3-Polymethylenequinolines and related compounds (review)

The methods for the synthesis of and the chemical properties and biological activity of 2, 3-polymethylenequinolines and related β-quinindines are reviewed.     

气相色谱-串联质谱法测定得克隆及其相关化台物在土壤样品中的含量

建立了得克隆(DP)及其脱氯产物和结构类似物等共11种化合物的气相色谱-串联质谱联用分析方法,并用于环境土壤中目标物的分析和污染特征研究.土壤样品抽提液经多段硅胶-氧化铝柱净化后,采用如下仪器条件分析:电子轰击电离源;选择反应离子对监测模式;DB-5HT毛细管柱(15 m×0.25 mm i.d.,0.1μm);进样口温度260℃,传输线温度280℃,离子源温度250℃;无分流进样1μL,载气为氦气(1.5 mL/min).实验结果表明,测定DP及其相关化合物的标准曲线线性范围为4~5个数量级,线性相关系数在0.9977~0.9999之间,仪器检出限在0.005~0.100 pg之间,方法检出限为0.25~5.00 fg/g,50 pg/μL标准样品平行5次进样的相对标准偏差(RSD)为1.1%~19.8%.对某典型污染区及其周边地区土壤进行分析,其中DP及相关化合物的总浓度在0.275~681 ng/g dw之间,检出率100%;单个目标物浓度在n.d.~537 ng/g dw之间,其中anti-DP和syn-DP为优势污染物,样品及质控样品中两种回收率指示物的加标回收率分别为55.0%~103.0%和83.4%~107.0%,空白/基质加标样品中目标物的平均回收率和RSD分别为53.9%~117.0%和6.0%~19.1%.     

Recent advances in the mass spectrometric analysis related to endocrine disrupting compounds in aquatic environmental samples

An overview of mass spectrometric methods used for the determination of endocrine disrupting compounds (EDCs) in environmental samples is presented. Among the EDCs we have selected five groups of compounds that are of priority within European Union and US research activities: alkylphenols, polychlorinated compounds (dioxins, furans and biphenyls), polybrominated diphenyl ethers, phthalates and steroid sex hormones. Various aspects of current LC-MS and GC-MS methodology, including sample preparation, are discussed.     

Dechlorane Plus in eggs of two gull species (Larus michahellis and Larus audouinii) from the southwestern Mediterranean Sea

Dechlorane Plus (DP) and some of its possible degradation products were measured in eggs from the yellow-legged gull (Larus michahellis) and Audouin's gull (Larus audouinii) from a protected area in the southwestern Mediterranean Sea. Statistically significant differences were found between both gull species, with yellow-legged gull eggs showing the highest average total DP concentration (209?pg/g wet weight). According to stable nitrogen and carbon isotope values, variations in DP concentrations in the gull species studied are explained by foraging behavior and diet rather than by the trophic position. Both DP stereoisomers were quantified in all the samples studied, and a slight enrichment of the anti-DP could have occurred in both species. The quantification of anti-[DP-1Cl] only in ～58?% of yellow-legged gulls support the hypothesis of a species-dependent factor influencing the bioaccumulation and/or biotransformation of Dechlorane-related compounds. This study reports on the first measurements of Dechlorane-related compounds in biota from the North African continent, contributing to the knowledge about DP environmental fate and distribution. In the light of our results, more research on differences in species-dependent bioaccumulation and biotransformation capabilities as well as ecological effects is encouraged in future Dechlorane-related compound studies.     

A critical review of the bioavailability of glucosinolates and related compounds

Glucosinolates (GLSs) are relatively inert (Z)-N-hydroximinosulfate esters, possessing a sulfur-linked beta-D-glucopyranose moiety and a variable side chain, found almost exclusively in cruciferous vegetables. Following cell disruption, they are hydrolysed by plant myrosinases, forming a group of chemically reactive and biologically active compounds. There is considerable evidence that these breakdown products, when consumed in the diet, may affect the risk of developing chronic diseases. However, in order for any compound to exert an activity in vivo, it is necessary to reach the site of action in an appropriate form and sufficient concentration. Deleterious and toxic effects may be observed at high concentrations: hence, bioavailability is a key factor defining the physiological, beneficial dose window of GLS hydrolysis products (GLS-HPs). For some GLS-HPs, this window can be rather narrow, and therefore is a critical parameter to be considered. In this review we critically evaluate the present state of knowledge on all factors that affect bioavailability of GLS-HPs. This includes liberation from the plant material, absorption from the digestive system, distribution around the body, metabolism and excretion.     

Chromium stress induced alterations in biochemical and enzyme metabolism in aquatic and terrestrial plants

Water is seriously polluted by the discharge of various industrial wastewater containing heavy metals. Among them, chromium is considered to be toxic to living organisms and it is released mostly from tanneries. The chromium-contaminated water is discharged into nearby water bodies and it affects both aquatic and terrestrial plants. So the present experiment was conducted with an aquatic plant, water lettuce (Pistia stratiotes L.) and a terrestrial plant soybean (Glycine max L. Merr.). They were treated with different concentrations (0, 5, 10, 25, 50, 100 and 200mg/L) of potassium dichromate solution. The biochemical parameters such as total chlorophyll, carotenoid, protein and amino acid content and the enzymatic activities like catalase and peroxidase were estimated. The accumulation of chromium was also analysed in both the plants. All the biochemical contents and enzyme activities of water lettuce and soybean seedlings showed a great variation with respect to the increase in chromium concentrations. The accumulation of chromium increased gradually with the increase of chromium concentrations. Total inhibition of all the parameters were observed at 300 mg/L chromium concentration. The terrestrial plant soybean was sensitive than the aquatic plant water lettuce towards chromium stress.     

Botrylactone: new interest in an old molecule—review of its absolute configuration and related compounds

The absolute configuration of botrylactone, a unique compound with an interesting polyketide lactone skeleton with two oxirane bridges previously isolated from Botrytis cinerea and described as a powerful antibiotic, has been reviewed on the basis of sign of the optical rotation, NOE experiments and NMR method. The isolation of 7-deoxybotrylactone and 5-hydroxy-7-(4-hydroxydec-2(3)-enoyl) botrylactone enables us to characterize an intriguing new family of compounds with this interesting polyketide skeleton. A common biosynthetic origin with botcinin derivatives is proposed.     

Arsenic compounds in marine and terrestrial organisms: Analytical,chemical and biochemical aspects

Arsenic has a reputation as a poison, because arsenic trioxide was used during medieval times as an agent for murder. Lingering memories of these events make any arsenic-containing material suspect. Toxicity is a property of a specific compound and varies with the composition and structure of compounds. Developments in analytical methodology made it possible not only to determine total arsenic in a variety of matrices but also arsenic compounds. Knowledge about the arsenic cycle in marine systems has expanded considerably during the past decade. The marine arsenic cycle appears to be more complex than the cycle in the terrestrial environment. More attention must be given to the minor arsenic-containing compounds detected in organisms and experiments should be undertaken that provide information about the biochemical pathways used for the transformation of arsenic compounds.     

Benzoxazines and related compounds

The reaction of 2-mercapto(and benzylthio)-α,α-dialkylbenzyl alcohols with nitriles under the influence of acids serves as a method for the synthesis of 2,4,4-trisubstituted 4H-1,3-benzothiazines.