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The use of nanotechnology-based products is constantly increasing and there are concerns about the fate and effect on the aquatic environment of antimicrobial products such as silver nanoparticles. By combining different characterization techniques (asymmetric flow field-flow fractionation, single particle ICP-MS, UV-Vis) we show that it is possible to assess in detail the agglomeration process of silver nanoparticles in artificial seawater. In particular we show that the presence of alginate or humic acid differentially affects the kinetic of the agglomeration process. This study provides an experimental methodology for the in-depth analysis of the fate and behaviour of silver nanoparticles in the aquatic environment., (Copyright © 2015. Published by Elsevier Ltd.)

Pet cats and dogs have been successfully used as indicators of environmental pollution by a great variety of chemicals, including metals. However, information on mercury (a well know priority environmental pollutant) concentrations in household pets tissues and/or organs is scarce. Thus, in the present work we quantified total mercury (Hg(Total)) in blood and hair samples from twenty-six household dogs. The obtained results disclose relatively low levels of total mercury in the surveyed dogs, with values ranging from 0.16 to 12.38 ng g(-1) in blood; and from 24.16 to 826.30 ng g(-1) in hair. Mercury concentrations were independent of gender, age and diet type. A highly significant positive correlation was established between total mercury in blood and hair, validating the latter as a surrogate, non-invasive matrix for mercury exposure evaluation. Additionally, the obtained blood to hair ratio (200) is similar to the one described for humans reinforcing the suitability of dogs as sentinels. Overall, the determination of total mercury levels in dogs' hair samples proved to be a good screening method for the estimation of mercury burden in this species. We propose the quantification of Hg(Total) in hair as a screening method for sentinels like household pets to be performed in routine veterinary visits.

Studies investigating the use of biomarkers in pesticide risk assessment have greatly increased in recent years; however, issues concerning the ecological meaning of enzymatic responses have proved controversial. Ideally a good biomarker response should be modulated by the environmental contaminants alone and demonstrate a predictable behavior towards certain types of toxins. As these premises are rarely observed, the present study aims to outline research that has contributed to an understanding of the behavior of two widely used biomarkers, cholinesterase and glutathione-S-transferase, describing environmental and biotic factors that affect their response in freshwater invertebrates. Studies were performed in the main classes of aquatic invertebrates with these biomarkers and conclusions were reached concerning their behavior towards the main classes of pesticides. Links between biomarker responses and conventional endpoints were evaluated so that ecological relevance could be attributed to enzymatic responses. Toxicity of mixtures was investigated, and cases of synergism and antagonism were pointed out as factors changing the expected toxicity of aquatic systems and leading to misinterpretations of biomarker responses. Finally, the use of biomarkers as a tool for biomonitoring and in situ assays was investigated, with discussion of advantages and disadvantages of their use.

In this study, a tree (Populus nigra L.) has been presented as data logger of mercury release in aquatic environments using tree rings chemistry to provide chronological historical monitoring of mercury discharge from a chlor-alkali industrial effluent to a coastal lagoon. Tree rings (Populus nigra L.) as mercury data logger is suggested by mercury accumulation trends in the tree rings reflecting the industrial plant capacity increments in the early stages of mercury discharges and enhancing industrial plant controls to minimize mercury discharges in the last two decades after imposed global regulations on mercury emissions.

A bioassay with Chironomus riparius larvae, using larval development and growth as endpoints, was carried out inside a rice field and in the adjacent wetland channel in Portugal, during pesticide treatments (molinate, endosulfan and propanil) to determine impact caused by pesticide contamination in freshwater ecosystems. The bioassay was also performed under laboratory conditions, to assess whether in situ and laboratory bioassays demonstrated comparable results. Growth was inhibited by concentrations of endosulfan (2.3 and 1.9 microgL(-1) averages) in water from rice field in both the field and laboratory, and by concentrations of endosulfan (0.55 and 0.76 microgL(-1) averages) in water from the wetland channel in the laboratory bioassay, while development was not affected. C. riparius larvae were not affected by molinate and propanil concentrations. The results indicate that endosulfan treatments in rice fields may cause an ecological impairment in adjacent freshwater ecosystems. The results also indicate that laboratory testing can be used to assess in situ toxicity caused by pesticide contamination.

As a result of mining activities the exposure of metal sulphides to oxidation takes place with consequent release of acid mine drainage (AMD). Biomonitoring instruments have been proven to have the best deterrent effect upon polluters. A new approach in online biomonitoring, with the Multispecies Freshwater Biomonitortrade mark (MFB), was developed combining behavioural and feeding responses of the Portuguese indigenous benthic shredder, Echinogammarus meridionalis (Pinkster, 1973) (Crustacea, Amphipoda). These endpoints, along with mortality, were measured and analyzed for a gradient of sublethal doses of AMD. Original river water was used as the control and three doses of treatments were attained by adding increasing volumes of AMD to the control. The increase in AMD concentration and concomitant decrease in pH and increase in the concentration of most metals was followed by an overall increase of the mortality, decrease of locomotion/feeding activity and inhibition of the feeding rate. Mortality was observed in the two highest concentrations of AMD. Significant decrease in average locomotion/feeding activity took place in the second treatment. Although an inhibition of feeding was observed along the gradient of AMD concentration only in the highest concentration the feeding rate was significantly reduced.

Single species responses have the potential to measure impacts at earlier stages than more traditional methods based in community structure. This study evaluates a bioassay with biological (survival, development, growth) and functional (post-exposure feeding rate) responses of Chironomus riparius larvae to assess water quality and contamination in rivers. The bioassay with C. riparius third instar larvae was performed, in autumn and spring, in reference sites and in organic and metal contaminated sites in Portuguese rivers. Biotic, physical and chemical parameters were determined for each site. The relationship between both bioassays responses and biotic indices (IBMWP and IASPT) and the physical and chemical parameters of respective sites were determined. In general biotic indices were able to discriminate between contaminated and not contaminated sites although they demonstrated a poor ability to detect low level of metal contamination during autumn. IASPT was negatively related to ammonia concentrations in both seasons. No significant differences in survival and post-exposure feeding rate were found between sites. Development was inhibited in the most metal contaminated site during autumn, but pH and ammonia concentrations in water accounted for 82% of developmental variation during this season. Growth was highly inhibited in the most metal contaminated site during both seasons. In autumn, growth was also inhibited in the low metal contaminated site and, during this season, pH and Mn and Fe concentrations in water samples accounted for 97% of growth variation between sites. The results suggest that in situ bioassay with C. riparius larvae using growth as the endpoint is a responsive and suitable tool that can be used as bioindicator of metal pollution and to biomonitor water quality in metal contaminated rivers.

The degradation of estuaries is a result of human activities which overloads the environment with substances of both industrial and/or natural origins. Bioindicators have been consistently used to interpret effects of contaminants in the environment. In this study, the use of biomarkers (particular measurable characteristics of a bioindicator organism) was used to evaluate the contamination by xenobiotics of Crangon crangon natural populations. The central aim was to evaluate the capability of a battery of biomarkers to discriminate sites with different types of contamination. The activity of the enzymes cholinesterases (ChE), lactate dehydrogenase (LDH) and glutathione S-transferases (GST) were used as biomarkers. In addition, the ChE form(s) present in the cephalotorax of C. crangon were characterised. Organisms were seasonally sampled from winter 2001/2002 to autumn of 2002, at "reference" sites and at sites that receive agricultural, industrial and/or urban effluents. Results obtained in the characterisation of ChE with different substrates and selective inhibitors demonstrate that the form of ChE present in the cephalotorax of C. crangon shows proprieties of vertebrates' AChE and therefore it may be classified as true AChE-like ChE. The battery of biomarkers exhibited seasonal and local variations, apparently related to agricultural, industrial or urban effluent contamination. The tested biomarkers proved to be able to discriminate sources of environmental contamination, and confirms C. crangon as a sensitive species suitable to be used as a bioindicator.