Nanoscale materials and their use in water contaminants removal—a review

Water scarcity is being recognized as a present and future threat to human activity and as a consequence water purification technologies are gaining major attention worldwide. Nanotechnology has many successful applications in different fields but recently its application for water and wastewater treatment has emerged as a fast-developing, promising area. This review highlights the recent advances on the development of nanoscale materials and processes for treatment of surface water, groundwater and industrial wastewater that are contaminated by toxic metals, organic and inorganic compounds, bacteria and viruses. In addition, the toxic potential of engineered nanomaterials for human health and the environment will also be discussed.     

Influence of tobacco smoke on carcinogenic PAH composition in indoor PM10 and PM2.5

Because of the mutagenic and/or carcinogenic properties, Polycyclic Aromatic Hydrocarbons (PAH), have a direct impact on human population. Consequently, there is a widespread interest in analysing and evaluating the exposure to PAH in different indoor environments, influenced by different emission sources. The information on indoor PAH is still limited, mainly in terms of PAH distribution in indoor particles of different sizes; thus, this study evaluated the influence of tobacco smoke on PM₁₀ and PM_2.5 characteristics, namely on their PAH compositions, with further aim to understand the negative impact of tobacco smoke on human health. Samples were collected at one site influenced by tobacco smoke and at one reference (non-smoking) site using low-volume samplers; the analyses of 17 PAH were performed by Microwave Assisted Extraction combined with Liquid Chromatography (MAE–LC). At the site influenced by tobacco smoke PM concentrations were higher 650% for PM₁₀, and 720% for PM_2.5. When influenced by smoking, 4 ring PAH (fluoranthene, pyrene, and chrysene) were the most abundant PAH, with concentrations 4600–21 000% and 5100–20 800% higher than at the reference site for PM₁₀ and PM_2.5, respectively, accounting for 49% of total PAH (Σ_PAH). Higher molecular weight PAH (5–6 rings) reached concentrations 300–1300% and 140–1700% higher for PM₁₀ and PM_2.5, respectively, at the site influenced by tobacco smoke. Considering 9 carcinogenic PAH this increase was 780% and 760% in PM₁₀ and PM_2.5, respectively, indicating the strong potential risk for human health. As different composition profiles of PAH in indoor PM were obtained for reference and smoking sites, those 9 carcinogens represented at the reference site 84% and 86% of Σ_PAH in PM₁₀ and PM_2.5, respectively, and at the smoking site 56% and 55% of Σ_PAH in PM₁₀ and PM_2.5, respectively. All PAH (including the carcinogenic ones) were mainly present in fine particles, which corresponds to a strong risk for cardiopulmonary disease and lung cancer; thus, these conclusions are relevant for the development of strategies to protect public health.     

Immunosuppression in the infaunal bivalve Scrobicularia plana environmentally exposed to mercury and association with its accumulation

This study aimed to test the hypothesis whether mercury (Hg) activates or suppresses inappropriately the immunity of the bivalve Scrobicularia plana inhabiting a Hg contaminated area (Laranjo basin, Ria de Aveiro, Portugal). Immunity endpoints, as well as lipid peroxidation (LPO) as a sign of damage, were evaluated in parallel with total Hg burden. Bivalves from both moderately (MO) and highly (HI) contaminated sites displayed higher haemolymph Hg load and reduced plasma agglutination. Increased haemocytes density and decreased phagocytosis were observed at HI, whereas increased oxidative burst activity (OBA) was observed at MO, pointing out that the immunotoxicity is a result of Hg direct contact involving no ROS intervention. OBA observed at MO was concomitantly associated to peroxidative damage as depicted by LPO increase in haemocytes and haemolymph plasma. Thus, S. plana can be suggested as a suitable bioindicator of metal pollution in coastal areas on the basis of Hg bioaccumulation and immunotoxicity responses.     

Redistribution of free tropospheric chemical species over West Africa: radicals (OH and HO₂), peroxide (H₂O₂) and acids (HNO₃ and H₂SO₄)

The purpose of this paper is to study the redistribution of chemical species (OH, HO₂, H₂O₂, HNO₃ and H₂SO₄) over West Africa, where the cloud cover is ubiquitously present, and where deep convection often develops. In this area, because of these cloud systems, chemical species are redistributed by the ascending and descending flow, or leached if they are soluble. So, we carry out a mesoscale study using the Regional Atmospheric Modelling System (RAMS) coupled to a code of gas and aqueous chemistry (RAMS_Chemistry). It takes into account all processes under mesh. We examine several cases following the period (November and July), with inputs emissions (anthropogenic, biogenic and biomass burning). The radicals OH and HO₂ are an indicator of possibilities for chemical activity. They characterize the oxidizing power of the atmosphere and are very strong oxidants. The acids HNO₃ and H₂SO₄ are interesting in their transformation into nitrates and sulfates in precipitation. In November, when photochemistry is active during an event of biomass burning, concentrations of chemical species are higher than those of November in the absence of biomass burning. The concentrations of nitric acid double and sulfuric acid increases 70 times. In addition, the concentrations are even lower in July if there is a deep convection. Compared to measures of the African Monsoon Multidisciplinary Analysis (AMMA), the results and observations of radicals OH and HO₂ are the same order of magnitude. Emissions from biomass burning increase the concentrations of acid and peroxide, and a deep convection cloud allows the solubility and the washing out of species, reducing their concentration. Rainfalls play a major role in solubility and washing out acids, peroxides and radicals in this region.     

Distribution of antidepressants and their metabolites in brook trout exposed to municipal wastewaters before and after ozone treatment--evidence of biological effects

This study examined the tissues distribution of selected serotonin reuptake inhibitors (SSRIs) in brook trout exposed for 3 months to continuous flow-through primary-treated effluent before and after ozone treatment. A reliable analytical method was developed for the quantification of trace amounts of antidepressants in small tissue homogenate extracts. Levels of six antidepressants and four of their N-desmethyl metabolites were determined using liquid chromatography-tandem mass spectrometry. Significant amounts of the SSRIs were found in fish tissue-in decreasing order: liver>brain>muscle. Sertraline and its metabolite desmethylsertraline were the predominant substances observed in most tissues (0.04-10.3 ng g(-1)). However, less SSRIs (0.08-1.17 ng g(-1)) were bioaccumulated in the ozonated effluent. The early molecular effects of these SSRIs on the Na/K-dependent ATPase pump activity in brain synaptosomes where also investigated in vitro and in fish exposed to the municipal effluents. With respect to their potential biological effects, in vitro exposure to selected SSRIs induced a reduction of the brain Na/K-ATPase activity in synaptosomes in a dose-dependent manner. Results showed that Na/K-ATPase activity was readily inhibited by exposure to municipal effluent before and, to a lesser extent, after ozone treatment. Moreover, the Na/K-ATPase activity was significantly and negatively correlated with brain tissue concentrations of fluoxetine (r=-0.57; p<0.03), desmethylsertraline (r=-0.84; p<0.001), and sertraline (r=-0.82; p<0.001). The present study reveals that SSRIs are readily available in fish, biologically active and corroborates previous findings on the serotonergic properties of municipal effluents to aquatic organisms.     

Evaluating pharmaceuticals and caffeine as indicators of fecal contamination in drinking water sources of the Greater Montreal region

We surveyed four different river systems in the Greater Montreal region, upstream and downstream of entry points of contamination, from April 2007 to January 2009. The studied compounds belong to three different groups: PPCPs (caffeine, carbamazepine, naproxen, gemfibrozil, and trimethoprim), hormones (progesterone, estrone, and estradiol), and triazine herbicides and their metabolites (atrazine, deethylatrazine, deisopropylatrazine, simazine, and cyanazine). In the system A, B, and C having low flow rate and high TOC, we observed the highest detection frequencies and mass flows of PPCPs compared to the other compounds, reflecting discharge of urban contaminations through WWTPs and CSOs. However, in River D, having high flow rate and low TOC, comparable frequency of detection of triazine and their by-products and PPCPs, reflecting cumulative loads of these compounds from the Great Lakes as well as persistency against natural attenuation processes. Considering large differences in the removal efficiencies of caffeine and carbamazepine, a high ratio of caffeine/carbamazepine might be an indicative of a greater proportion of raw sewage versus treated wastewater in surface waters. In addition, caffeine appeared to be a promising indicator of recent urban fecal contaminations, as shown by the significant correlation with FC (R² = 0.45), while carbamazepine is a good indicator of cumulative persistence compounds.     

Impact of water quality on bacterioplankton assemblage along Cértima River Basin (central western Portugal) assessed by PCR–DGGE and multivariate analysis

The information on bacterial community composition (BCC) in Portuguese water bodies is very scarce. Cértima River (central western Portugal) is known to have high levels of pollution, namely organic. In the present work, the BCC from a set of 16 water samples collected from Cértima River Basin and its main tributaries was characterized using 16S rDNA–denaturing gradient gel electrophoresis, a culture-independent molecular approach. Molecular data were related to environmental parameters through multivariate analysis to investigate potential impact of water pollution along the river. Principal component analysis using environmental data showed a water quality gradient from more pristine waters (at the mountain tributaries) to waters with increasingly eutrophic potential (such as Fermentelos Lake). This gradient was mainly defined by factors such as organic and inorganic nutrient sources, electrical conductivity, hydrogen carbonate concentration, and pH. Molecular results showed variations in BCC along Cértima River Basin but in the main river section, a Bacteroidetes phylotype (Flavobacterium sp.) proved to be dominant throughout the river course. Multivariate analysis suggests that spatial variation of BCC along the Cértima River Basin depended mainly on parameters such as Chl a, total suspended solid (TSS), total organic carbon, electrical conductivity, and HCO _boxclose^-_{3}^{-} levels. Bacteroidetes phylotypes were all related to higher electrical conductivity and HCO₃^-_{3}^{-} levels although some of these were also correlated with high SO₄^2-_{4}^{2-} and others with high soluble reactive phosphorus, nitrate, TN, and Kjeld-N levels. The Gammaproteobacteria occurrence was correlated with high SO₄^2-_{4}^{2-} levels. One of the Betaproteobacteria phylotypes showed to correlate with low redox potential (E_h) and high temperature, pH, TSS, and Chl a levels while another one showed a negative correlation with Chl a values.     

Environmental monitoring of alcohol sulfates and alcohol ethoxysulfates in marine sediments

The study describes the environmental monitoring of anionic surfactants―alcohol sulfates (AS) and alcohol ethoxysulfates (AES)—in marine sediments. Concentration values were obtained after pressurised liquid extraction (PLE) and liquid chromatography–tandem mass spectrometry analysis (LC–MS/MS). Samples were collected from a range of wastewater discharge points along the coast of the provinces of Huelva, Málaga, Granada and Almería. Urban, agricultural and industrial wastewaters are discharged at the selected 38 sampling sites. Principal component analysis was carried out in order to evaluate the distribution and behaviour of these compounds in these coastal environments. Evaluation of the data revealed that the behaviour and sources of AS and AES in marine sediments are different, and that the distribution of AES depends on the length of the alkyl chain, while the number of ethoxylated units is not relevant. Additionally, the 38 sampling sites can be grouped into only two types of outfalls according to their AS distribution. The concentration of compounds in sediment samples ranged from 7.52 to 13.50 mg kg^?1 for AS, from 3.04 to 10.68 mg kg^?1 for AES–C₁₂E_x and from 3.83 to 11.56 mg kg^?1 for AES–C₁₄E_x.     

Brominated flame retardants and organochlorines in the European environment using great tit eggs as a biomonitoring tool

Large-scale studies are essential to assess the emission patterns and spatial distribution of organohalogenated pollutants (OHPs) in the environment. Bird eggs have several advantages compared to other environmental media which have previously been used to map the distribution of OHPs. In this study, large-scale geographical variation in the occurrence of OHPs, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs), was investigated throughout Europe using eggs of a terrestrial residential passerine species, the great tit (Parus major). Great tit eggs from 22 sampling sites, involving urban, rural and remote areas, in 14 European countries were collected and analysed (5-8 eggs per sampling site). The environmentally most important congeners/compounds of the analysed pollutants were detectable in all sampling locations. For PCBs, PBDEs and OCPs, no clear geographical contamination pattern was found. Sum PCB levels ranged from 143 ng/g lipid weight (lw) to 3660 ng/g lw. As expected, PCB concentrations were significantly higher in the sampled urban compared to the remote locations. However, the urban locations did not show significantly higher concentrations compared to the rural locations. Sum PBDEs ranged from 4.0 ng/g lw to 136 ng/g lw. PBDEs were significantly higher in the urbanized sampling locations compared to the other locations. The significant, positive correlation between PCB and PBDE concentrations suggests similar spatial exposure and/or mechanisms of accumulation. Significantly higher levels of OCPs (sum OCPs ranging from 191 ng/g lw to 7830 ng/g lw) were detected in rural sampling locations. Contamination profiles of PCBs, PBDEs and OCPs differed also among the sampling locations, which may be due to local usage and contamination sources. The higher variance among sampling locations for the PCBs and OCPs, suggests that local contamination sources are more important for the PCBs and OCPs compared to the PBDEs. To our knowledge, this is the first study in which bird eggs were used as a monitoring tool for OHPs on such a large geographical scale.     

PAH air pollution at a Portuguese urban area: carcinogenic risks and sources identification

This study aimed to characterize air pollution and the associated carcinogenic risks of polycyclic aromatic hydrocarbon (PAHs) at an urban site, to identify possible emission sources of PAHs using several statistical methodologies, and to analyze the influence of other air pollutants and meteorological variables on PAH concentrations.The air quality and meteorological data were collected in Oporto, the second largest city of Portugal. Eighteen PAHs (the 16 PAHs considered by United States Environment Protection Agency (USEPA) as priority pollutants, dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were collected daily for 24 h in air (gas phase and in particles) during 40 consecutive days in November and December 2008 by constant low-flow samplers and using polytetrafluoroethylene (PTFE) membrane filters for particulate (PM₁₀ and PM_2.5 bound) PAHs and pre-cleaned polyurethane foam plugs for gaseous compounds. The other monitored air pollutants were SO₂, PM₁₀, NO₂, CO, and O₃; the meteorological variables were temperature, relative humidity, wind speed, total precipitation, and solar radiation. Benzo[a]pyrene reached a mean concentration of 2.02 ng?m^?3, surpassing the EU annual limit value. The target carcinogenic risks were equal than the health-based guideline level set by USEPA (10^?6) at the studied site, with the cancer risks of eight PAHs reaching senior levels of 9.98?×?10^?7 in PM₁₀ and 1.06?×?10^?6 in air. The applied statistical methods, correlation matrix, cluster analysis, and principal component analysis, were in agreement in the grouping of the PAHs. The groups were formed according to their chemical structure (number of rings), phase distribution, and emission sources. PAH diagnostic ratios were also calculated to evaluate the main emission sources. Diesel vehicular emissions were the major source of PAHs at the studied site. Besides that source, emissions from residential heating and oil refinery were identified to contribute to PAH levels at the respective area. Additionally, principal component regression indicated that SO₂, NO₂, PM₁₀, CO, and solar radiation had positive correlation with PAHs concentrations, while O₃, temperature, relative humidity, and wind speed were negatively correlated.