Patrícia S.M. Santos

(Nano)plastics in the environment - Sources, fates and effects.

Abstract There has been a considerable increase on research of the ecological consequences of microplastics released into the environment, but only a handful of works have focused on the nano-sized particles of polymer-based materials. Though their presence has been difficult to adequately ascertain, due to the inherent technical difficulties for isolating and quantifying them, there is an overall consensus that these are not only present in the environment – either directly released or as the result of weathering of larger fragments – but that they also pose a significant threat to the environment and human health, as well. The reduced size of these particulates ( In this review, we describe the most relevant sources of nanoplastics and offer some insights into their fate once released into the environment. Furthermore, we overview the most prominent effects of these small particulates, while identifying the key challenges scientists currently face in the research of nanoplastics in the environment. Lastly, we give a brief summary of the economic impacts of the pollution caused by plastic litter – a potential key source of nanoplastics – in the oceans, the most common destination of these contaminants.

Spectroscopic characterization of dissolved organic matter isolated from rainwater

Rainwater is a matrix containing extremely low concentrations (in the range of muM C) of dissolved organic carbon (DOC) and for its characterization, an efficient extraction procedure is essential. A recently developed procedure based on adsorption onto XAD-8 and XAD-4 resins in series was used in this work for the extraction and isolation of rainwater dissolved organic matter (DOM). Prior to the isolation and fractionation of DOM, and to obtain sufficient mass for the spectroscopic analyses, individual rainwater samples were batched together according to similar meteorological conditions on a total of three composed samples. The results of the isolation procedure indicated that the resin tandem procedure is not applicable for rainwater DOM since the XAD-4 resin caused samples contamination. On the other hand, the XAD-8 resin allowed DOM recoveries of 39.9-50.5% of the DOC of the original combined samples. This recovered organic fraction was characterized by UV-visible, molecular fluorescence, FTIR-ATR and 1H NMR spectroscopies. The chemical characterization of the rainwater DOM showed that the three samples consist mostly of hydroxylated and carboxylic acids with a predominantly aliphatic character, containing a minor component of aromatic structures. The obtained results suggest that the DOM in rainwater, and consequently in the precursor atmospheric particles, may have a secondary origin via the oxidation of volatile organic compounds from different origins.

First spectroscopic study on the structural features of dissolved organic matter isolated from rainwater in different seasons

The complexity of rainwater dissolved organic matter (DOM) and the large percentage considered uncharacterized has made it difficult to determine the role of rainwater DOM in regional and global carbon budgets. Recent studies have concentrated on determining the structural characteristics of the bulk DOM in rainwater, but a comparison between the structural characteristics of rainwater DOM from different seasons is lacking. In this work, DOM was extracted from rainwater collected in different seasons by a procedure based on adsorption onto DAX-8 resin and a comparison between the spectroscopic characteristics of extracted DOM was performed using UV-visible, excitation-emission matrix (EEM) fluorescence and (1)H NMR spectroscopies. Similar structural characteristics were observed for extracted DOM from the different seasons: high content of aliphatic structures, hydroxy and alkoxy groups, carbonyl groups and unsaturated carbon atoms, and low content of aromatic structures when compared with aliphatic structures. The obtained results suggest a model of chemical structures for the extracted DOM from rainwater, as consisting mainly of aliphatic chains, with COOH, -CH(2)OH, -COCH(3), or -CH(3) terminal groups, and with only a minor aromatic component. Moreover, this study suggests that the DOM extracted from rainwater has higher aliphatic character and lower aromatic content than aquatic humic substances. Thus, the chemical characteristics of aquatic humic substances may not be good models for DOM extracted from rainwater.

Label-free disposable immunosensor for detection of atrazine

This work reports the construction of a fast, disposable, and label-free immunosensor for the determination of atrazine. The immunosensor is based on a field effect transistor (FET) where a network of single-walled carbon nanotubes (SWCNTs) acts as the conductor channel, constituting carbon nanotubes field effect transistors (CNTFETs). Anti-atrazine antibodies were adsorbed onto the SWCNTs and subsequently the SWCNTs were protected with Tween 20 to prevent the non-specific binding of bacteria or proteins. The principle of the immunoreaction consists in the direct adsorption of atrazine specific antibodies (anti-atrazine) to SWCNTs networks. After exposed to increasing concentrations of atrazine, the CNTFETs could be used as useful label-free platforms to detect atrazine. Under the optimal conditions, a limit of detection as low as 0.001 ng mL(-1) was obtained, which is lower than that of other methods for the atrazine detection, and in a working range between 0.001 and 10 ng mL(-1). The average recoveries obtained for real water samples spiked with atrazine varied from 87.3% to 108.0%. The results show that the constructed sensors display a high sensitivity and could be useful tools for detecting pesticides like atrazine at low concentrations. They could be also applied to the determination of atrazine in environmental aqueous samples, such as seawater and riverine water.

Chemical composition of rainwater at a coastal town on the southwest of Europe: what changes in 20 years?

Rainwater was collected at the Portuguese west coast between September 2008 and September 2009, and analysed for pH, conductivity, and Cl⁻, NO₃⁻, SO₄²⁻, and NH₄⁺ concentrations. Results of rainwater chemical composition were compared with those obtained at the same site between 1986 and 1989. In both collection periods rainwater was predominantly (≈ 80%) associated to oceanic air masses. The rainwater concentration of H⁺ was in the same range as twenty years ago. A clear decrease of non sea salt sulphate (NSS-SO₄²⁻) was observed in 2008-2009 relatively to 1986-1989, not only in samples with origin in central and northern Europe, but also in samples from Atlantic Ocean and Mediterranean. This decrease indicates that SO₂ emissions were reduced, which may be due to a lower content of sulphur in oil by-products. A decrease was also observed in NH₄⁺ concentration in 2008-2009. On the contrary an increase of NO₃⁻ concentration was observed for samples of all origins in 2008-2009 relatively to 1986-1989, which was particularly high (more than 3 fold) for samples with origin in Atlantic Ocean, suggesting the incorporation of this ion by rainout at the sampling site. The contribution of local sources is indeed suggested by the moderate negative correlation of NH₄⁺, NO₃⁻ and NSS-SO₄²⁻ with rainwater volume. The high increase of NO₃⁻ concentration can be attributed to the increase of local vehicular and industrial emissions in the sampling area.

Comparison between DAX-8 and C-18 solid phase extraction of rainwater dissolved organic matter

Rainwater is a very low concentrated matrix and, for dissolved organic matter (DOM) characterization, an efficient extraction procedure is essential. Isolation procedures based on the adsorption onto XAD-8 and C-18 sorbents have been used in the literature for rainwater DOM isolation, but a comparison between these procedures is lacking. In this work, UV-visible and molecular fluorescence spectroscopies highlighted differences between rainwater DOM isolated by DAX-8 (replacement for XAD-8) and by C-18. It was possible to recover higher rainwater DOM percentage by the C-18 based procedure than by the DAX-8 one. Rainwater protein-like compounds were better concentrated by the C-18 procedure than by the DAX-8 one, while humic-like compounds were similarly concentrated by both procedures. Furthermore, rainwater DOM extracted by the C-18 procedure was more representative of the global matrix, while DAX-8 preferentially extracted humic-like compounds.

Biodegradation of polyethylene microplastics by the marine fungus Zalerion maritimum

Plastic yearly production has surpassed the 300milliontons mark and recycling has all but failed in constituting a viable solution for the disposal of plastic waste. As these materials continue to accumulate in the environment, namely, in rivers and oceans, in the form of macro-, meso-, micro- and nanoplastics, it becomes of the utmost urgency to find new ways to curtail this environmental threat. Multiple efforts have been made to identify and isolate microorganisms capable of utilizing synthetic polymers and recent results point towards the viability of a solution for this problem based on the biodegradation of plastics resorting to selected microbial strains. Herein, the response of the fungus Zalerion maritimum to different times of exposition to polyethylene (PE) pellets, in a minimum growth medium, was evaluated, based on the quantified mass differences in both the fungus and the microplastic pellets used. Additionally, molecular changes were assessed through attenuated total reflectance Fourier transform Infrared Spectroscopy (FTIR-ATR) and Nuclear Magnetic Resonance (NMR). Results showed that, under the tested conditions, Z. maritimum is capable of utilizing PE, resulting in the decrease, in both mass and size, of the pellets. These results indicate that this naturally occurring fungus may actively contribute to the biodegradation of microplastics, requiring minimum nutrients.

Molecular fluorescence analysis of rainwater: Effects of sample preservation

Very different filtration and preservation procedures may be found in the literature on the study of the rainwater dissolved organic fraction. Thus, the influence of sample filtration and preservation procedures on the fluorescence of rainwater dissolved organic matter (DOM) was studied in this work. Rainwater was filtered through different filters (quartz 0.22 microm or PVDF 0.45 microm) and excitation (lambda(em)=415 nm) and synchronous (Deltalambda=70 nm) fluorescence spectra were obtained at the same day of collection, or after preservation by refrigeration (1-7 days) or by freezing (1-4 weeks). The excitation-emission matrix (EEM) spectra of rainwater showed six types of fluorescent bands: two corresponding to humic-like bands, and four resembling proteins. Then, the excitation and synchronous spectra were chosen in order to monitor changes in the humic-like and protein-like bands, respectively. The filtration procedures adopted in this work did not affect the fluorescence properties of the rainwater samples. However, these properties were differently preserved by refrigeration or freezing: after refrigeration, filtered rainwater maintained the original fluorescent properties for at least 4 days, while after freezing fluorescent properties were not always preserved since it occurred a decrease of protein-like fluorescence intensity.

Dissolved organic and inorganic matter in bulk deposition of a coastal urban area: An integrated approach

Bulk deposition can remove atmospheric organic and inorganic pollutants that may be associated with gaseous, liquid or particulate phases. To the best of our knowledge, few studies have been carried out, which simultaneously analyse the presence of organic and inorganic fractions in rainwater. In the present work, the complementarity of organic and inorganic data was assessed, through crossing data of some organic [DOC (dissolved organic carbon), absorbance at 250 nm (UV250nm), integrated fluorescence] and inorganic [H(+), NH4(+), NO3(-), non sea salt sulphate (NSS-SO4(2-))] parameters measured in bulk deposition in the coastal urban area of Aveiro. The organic and inorganic parameters analysed were positively correlated (p<0.001) except for H(+), which suggests that a constant fraction of chromophoric dissolved organic matter (CDOM) came from anthropogenic sources. Furthermore, the inverse correlations observed for the organic and inorganic parameters with the precipitation amount suggest that organic and inorganic fractions were incorporated into the rainwater partially by below-cloud scavenging of airborne particulate matter. This is in accordance with the high values of DOC and NO3(-) found in samples associated with marine air masses, which were linked in part to the contribution of local emissions from vehicular traffic. DOC of bulk deposition was the predominant constituent when compared with the constituents H(+), NH4(+), NO3(-) and NSS-SO4(2-), and consequently bulk deposition flux was also highest for DOC, highlighting the importance of DOC and of anthropogenic ions being simultaneously removed from the atmosphere by bulk deposition. However, it was verified that the contribution of anthropogenic sources to the DOC of bulk deposition may be different for distinct urban areas. Thus, it is recommended that organic and inorganic fractions of bulk deposition are studied together.

Development of an electrochemical biosensor for alkylphenol detection.

In this work, electrochemical biosensors based on field effect transistors (FET) with single-walled carbon nanotubes (SWCNT) were constructed as disposable analytical devices to detect alkylphenols through immunoreaction using 4-nonylphenol (NP) as model analyte, and validated by comparison with enzyme-linked immunosorbent assay (ELISA). The calibration curve displays a working range with five concentrations between 5 and 500µgL(-1), and for each concentration, five biosensors were analysed for reproducibility estimation and two analytical measurements were performed for each biosensor for repeatability estimation. The accuracy of the biosensors was validated by analyzing NP contents in ten spiked artificial seawater samples and comparing these results to those obtained with the traditional ELISA methodology. Excellent analytical performance was obtained with reproducibility of 0.56±0.08%, repeatability of 0.5±0.2%, limit of detection for NP as low as 5µgL(-1), and average recovery between 97.8% and 104.6%. This work demonstrates that simple biosensors can be used to detect hazardous priority substances in seawater samples, even at low concentrations.