M. Ramiro Pastorinho

History on organotin compounds, from snails to humans

Organotin compounds are industrial chemicals used as biocides, polyvinyl chloride stabilizers and industrial catalysts for the manufacture of silicone and polyurethane foams. Despite multiple applications, organotin notoriety is due to tributyltin, a potent biocide used in antifouling paints. Because of the intensive use of tributyltin for the protection of ships’ hulls, tributyltin has been largely released into waters, resulting in adverse and even bizarre effects on aquatic organisms, such as imposex in gastropods. However, organotins include other compounds such as tributyltin derivatives, phenyltins and octyltins. Organotin use in plastics, silicone and foams results in their occurrence almost everywhere, e.g., clothes, toys, wallpaper, food containers, household piping and medical devices. Hence, humans are exposed to organotins not solely through ingestion of contaminated seafood but also through direct contact with treated products and by inhalation and ingestion of dust. As a consequence, organotins have been detected in human samples. Toxicity data reveal that organotins are endocrine disruptors, immunotoxicants, carcinogens and obesogens. Here, we review the levels, fate and effects of organotin compounds toward wildlife and humans, starting with a description of organotin applications, with particular incidence in antifouling paints. The global contamination of the marine environment and the deleterious effects of tributyltin onto nontarget organisms are addressed, with particular attention to the imposex phenomenon. The restrictions on tributyltin use in antifouling paints are also described alongside with the new regulations for organotins in consumer products. The sources and pathways of organotins in the environment are discussed, studies in human exposure are presented, and future research is proposed.

Ionic-liquid-based aqueous biphasic systems for improved detection of bisphenol A in human fluids

Bisphenol A is a human endocrine disruptor. Its normally low levels in biological fluids make it difficult to detect via conventional techniques. This work demonstrates the complete extraction of bisphenol A, and its possible concentration up to 100-fold in a single-step procedure, using ionic-liquid-based aqueous biphasic systems.

Metal(Loid) Levels in Biological Matrices from Human Populations Exposed to Mining Contamination—Panasqueira Mine (Portugal)

Mining activities may affect the health of miners and communities living near mining sites, and these health effects may persist even when the mine is abandoned. During mining processes various toxic wastes are produced and released into the surrounding environment, resulting in contamination of air, drinking water, rivers, plants, and soils. In a geochemical sampling campaign undertaken in the Panasqueira Mine area of central Portugal, an anomalous distribution of several metals and arsenic (As) was identified in various environmental media. Several potentially harmful elements, including As, cadmium (Cd), chromium (Cr), manganese (Mn), nickel (Ni), lead (Pb), and selenium (Se), were quantified in blood, urine, hair, and nails (toe and finger) from a group of individuals living near the Panasqueira Mine who were environmentally and occupationally exposed. A group with similar demographic characteristics without known exposure to mining activities was also compared. Genotoxicity was evaluated by means of T-cell receptor (TCR) mutation assay, and percentages of different lymphocyte subsets were selected as immunotoxicity biomarkers. Inductively coupled plasma–mass spectrometry (ICP-MS) and inductively coupled plasma–atomic emission spectrometry (ICP-AES) analysis showed elevated levels of As, Cd, Cr, Mn, and Pb in all biological samples taken from populations living close to the mine compared to controls. Genotoxic and immunotoxic differences were also observed. The results provide evidence of an elevated potential risk to the health of populations, with environmental and occupational exposures resulting from mining activities. Further, the results emphasize the need to implement preventive measures, remediation, and rehabilitation plans for the region.

An evaluation of trace metal distribution, enrichment factors and risk in sediments of a coastal lagoon (Ria de Aveiro, Portugal)

This paper describes a sediment survey undertaken to unravel patterns of distribution and dispersion of trace metals in an Iberian Peninsula northwestern coastal lagoon (Ria de Aveiro). Cadmium, lead, chromium, copper and zinc were analyzed in bottom sediments. Geochemical normalization is performed and two different regression models for each metal versus aluminum are tested and compared using the respective enrichment factors (EF), an estimation of the relative importance of anthropogenic contributions to the studied sediments. Mean sediment quality guideline quotients (mSQGQ) are used to evaluate sediment quality and associated potential risk to biota with effects range low as empirical sediment quality guideline (SQG) in the basis for mSQGQ calculation. Additionally, the geoaccumulation index is calculated to compare studied sediment levels to global baseline levels. The application of SQGs revealed insufficient characterization capability, especially when contrasted to EF calculated from the regression methods. These pointed a mildly enriched system with localized “hot spot” areas. Therefore, it can be considered that bottom sediments in the Ria de Aveiro system are in their majority unpolluted, zinc being the only metal of concern, presenting enrichment in all four main channels. The major rivers outlets (Caster, Antuã, and Vouga) constitute point sources, thus presenting potential risk for biota. Yet, the strong tidal influence creates a damping effect by efficiently redistributing sediment bound metals.

Amphipod susceptibility to metals: Cautionary tales

Heavy metals accumulated by aquatic crustaceans in environmental studies are normally investigated using the whole body burden, with little regard paid to uptake in different tissues, to potential gender of life stage differences, or to the influence of nutrition on the test organism. This is likely to give erroneous conclusions for a dose-response relationship within the toxicity test and potentially lead to wrong conclusions for the ecological risks of metals where species may have higher sensitivities with gender and life stage than indicated or that functionally metals may be sequestered into parts of the body so are not bioavailable. This could lead to under-estimation or over-estimation of the toxicity of metals, respectively, inaccuracy of metal budget calculations and evaluation of trophic transfers of metals. This study evaluated the influences of life stage, gender, and a priori nutritional state in the uptake of the metals zinc (an essential micro-nutrient; Zn) and cadmium (a non-essential element; Cd) in the amphipod Echinogammarus marinus. The study showed that life stage, and nutritional stage did significantly influence the uptake and bioaccumulation for both metals, but only Cd showed differential uptake and bioaccumulation with gender. In addition, it was concluded that there was a significant uptake and accumulation of both metals within the exoskeleton of the amphipods, which though adding to the full body burden would add little to toxicity through lack of bioavailability. These results showed that care should be taken when interpreting results from tests normally preformed on such test organisms.

Amphipod intersex, metals and latitude: A perspective

Intersexuality has been widely reported in crustaceans with several mechanisms being directly or indirectly held responsible for its occurrence, amongst which pollution. No mechanistic relationship between metals and intersex has ever been established. Also the incidence of intersex in populations of the same invertebrate species in a latitudinal gradient has never been studied so far. Three populations (Iceland, Scotland and Portugal) of the amphipod Echinogammarus marinus were scrutinized. Intersex females from Iceland registered the highest fecundity loss. Only in Scottish samples females with two genital papillae and males with only one genital papillae were observed. Nevertheless, water, biota and sediment samples pointed to equivalent metal levels, and in consonance the prevalence of intersex was not significantly different between locations. An unequivocal relationship between metal presence and intersex induction cannot be presented, but our results advocate the potential role of metals as a direct cause of intersexuality in E. marinus.

Levels of TBT and other selected organotin compounds in duplicate diet samples.

Organotin compounds (OTs) are ubiquitous contaminants with a broad range of applications ranging from biocides and pesticides to catalysts for the production of polyurethane foams and silicones. The deleterious effects of some OTs (particularly tributyltin - TBT) upon wildlife and experimental animals are well documented and include endocrine disruption, immunotoxicity, neurotoxicity, genotoxicity and metabolic dysfunction in which obesity is included. However, virtually no data on the current human exposure levels is available. In order to bridge this gap, we quantified for the first time the levels of OTs in duplicate diet samples from members of the University of Aveiro in Portugal. OTs were detected in 32% of the 28 diet samples analyzed, at relatively low levels. TBT and monobutyltin were detected only in two samples and dibutyltin was detectable in three samples. Dioctyltin was quantified in four samples and monooctyltin in three samples. Phenyltins were below the detection limit in all the diet samples analyzed. Overall, for the vast majority of the samples (89%), the estimated daily intakes (EDI) of organotins through food were much lower than the established tolerable daily intakes (TDI). Hence, for the majority of the participants the risk associated with food ingestion is low.

Organotin Compounds from Snails to Humans

Human activities are producing and transforming more than 140,000 chemical compounds according to the European Union Regulation REACH (registration, evaluation, authorization and restriction of chemicals). Humans and wildlife can be exposed to chemicals at all stages of the chemical life cycle: raw material extraction, manufacturing and processing, use, recycling or disposal. Some chemicals can mimic or antagonize hormone action, affecting the normal functioning of organisms. These chemicals, defined as endocrine disruptors, include among many other organotin compounds.

Urine protein-to-creatinine concentration ratio in samples collected by means of cystocentesis versus manual compression in cats

Objective-To compare urine protein-to-creatinine concentration (UPC) ratios in samples collected by means of cystocentesis versus manual compression in cats. Design-Evaluation study. Animals-43 client-owned cats requiring urinalysis. Procedures-In all cats, 5 mL of urine from the midstream phase of micturition was collected by means of manual compression and, subsequently, an additional 5 mL of urine was obtained by means of ultrasound-guided cystocentesis. A complete urinalysis was performed on all samples, and UPC ratios were determined. Results-Cats were classified on the basis of the International Renal Interest Society substaging system as being free from proteinuria (UPC ratio, < 0.2; n = 19) or as having borderline proteinuria (UPC ratio, 0.2 to 0.4; 7) or proteinuria (UPC ratio, > 0.4; 17). None of the cats had postrenal proteinuria. A significant linear correlation was identified between UPC ratios in urine samples obtained by means of manual compression and ratios in samples obtained by means of cystocentesis. For all cats, UPC ratios for samples obtained by the 2 collection methods resulted in classification in the same IRIS substage. Conclusions and Clinical Relevance-Results suggested that collection of a urine sample from the midstream phase of micturition by manual compression would be a reliable alternative to cystocentesis for the determination of UPC ratio in cats, provided that postrenal proteinuria was excluded by means of urine sediment analysis. Once postrenal proteinuria was ruled out, the method used to collect urine samples did not appear to influence the quantification of urine protein concentration.

Characterization of Fungal Communities in House Dust Samples Collected From Central Portugal—A Preliminary Survey

House dust is a repository and concentrator of many chemical and biological agents including fungi. Considering that dust acts as a long-term reservoir of airborne fungi and that cumulative exposure is more relevant to potential health problems than single-day or short-term exposure, characterization of fungal communities in dust samples is of paramount importance. In the present study, the fungal composition of Portuguese house dust samples was determined. A total of 28 samples were obtained from vacuum cleaner deposits from households located in central Portugal. DNA was extracted from dust samples and fungal communities were analyzed using a culture-independent polymerase chain reaction (PCR)– denaturing gradient gel electrophoresis (DGGE) approach. Cultural analyses were also performed in order to identify the viable fungi species present in selected samples. Fungal diversity, reported as the number of operational taxonomic units (OTU), varied between 9 and 56 OTU. This analysis of viable fungi showed that Aspergillus was the most abundant genus, followed by Penicillium, Mucor, and Rhizomucor. Trichoderma, Chrysosporium, Fusarium, Rhizopus, and Stachybotrys were found in a limited number of houses. Our results demonstrated that dust is, in fact, home for a diverse and heterogeneous fungal community and that some of the species found are known allergic agents with severe negative impacts on human health.