A Unique Monitoring Method for Fecal and Sewage-Derived Chemical Pollution Utilizing International Pellet Watch Approach.

This study established a unique approach to assess fecal contamination by measuring fecal sterols, especially coprostanol (5ß-cholestanol-3ß-ol, 5ß) and cholestanol (5α-cholestan-3ß-ol, 5α) and their ratio 5ß/(5ß + 5α) alongside triclosan (TCS) and methyl-triclosan (MTC) in beached plastic pellets across 40 countries. Coprostanol concentrations ranged from 3.6 to 8190 ng/g pellet with extremely high levels in densely populated areas in African countries. The 5ß/(5ß + 5α) ratio was not affected by the difference in residence time of pellets in aquatic environments, and their spatial pattern showed a positive correlation with that of sedimentary sterols, demonstrating its reliability as an indicator of fecal contamination. Pellets from populated areas of economically developing countries, i.e., Africa and Asia, with lower coverage of wastewater treatment exhibited higher 5ß/(5ß + 5α) ratios (∼0.7) corresponding to ∼1% sewage in seawater, while pellets from developed countries, i.e., the USA, Canada, Japan, and Europe, with higher coverage of modern wastewater treatment displayed lower ratios (∼0.5), corresponding to the first contact limit. Triclosan levels were higher in developing countries (0.4-1298 ng/g pellet), whereas developed countries showed higher methyl-triclosan levels (0.5-70 ng/g pellet) due to TCS conversion during secondary treatment. However, some samples from Japan and Europe displayed higher TCS levels, suggesting contributions from combined sewage overflow (CSO). Combination of 5ß/(5ß + 5α) and MTC/TCS ratios revealed extreme fecal contamination from direct input of raw sewage due to inadequate treatment facilities in some African and South and Southeast Asian countries.

Microplastic-sorbed persistent organic pollutants in coastal Mediterranean Sea areas of Tunisia.

Microplastics (MPs) are emerging pollutants of global concern due to their pervasiveness, high sorption ability for persistent organic pollutants (POPs) and direct and indirect toxicity to marine organisms, ecosystems, as well as humans. As one of the major coastal interfaces, beaches are considered among the most affected ecosystems by MPs pollution. The morphological characteristics of MPs (pellets and fragments) collected from four beaches along the Tunisian coast and sorbed POPs, including polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), were investigated in this study. The results showed that the MPs varied greatly in color, polymer composition and degradation degree. The color varied from colored to transparent and the most prevalent polymer identified using Raman spectroscopy was polyethylene. Scanning electron microscope (SEM) images exhibited various surface degradation features including cavities, cracks, attached diatom remains, etc. The concentrations of Σ12PCBs over all beaches ranged from 14 to 632 ng g-1 and 26 to 112 ng g-1 in the pellets and fragments, respectively, with a notable presence and dominance of highly-chlorinated PCBs such as CB-153 and -138. Among the OCPs, γ-HCH is the only compound detected with concentrations ranging from 0.4 to 9.7 ng g-1 and 0.7 to 4.2 ng g-1 in the pellets and fragments, respectively. Our findings indicate that MPs found on the Tunisian coast may pose a chemical risk to marine organisms as the concentrations of PCBs and γ-HCH in most of the analysed samples exceeded the sediment-quality guidelines (SQG), especially the effects range medium (ERM) and the probable effects level (PEL). As the first report of its kind, the information gathered in this study can serve as the baseline and starting point for future monitoring work for Tunisia and neighbouring countries, as well as for stakeholders and coastal managers in decision-making processes.

Diffuse reflectance spectroscopy (DRS) and infrared (IR) measurements for studying biofilm formation on common plastic litter polymer (LDPE and PET) surfaces in three different laboratory aquatic environments.

Different species of microorganisms colonize the plastic surfaces and form biofilms depending on the aquatic environment. In the current investigation, characteristics of the plastic surface after exposure to three different aquatic environments based on visualization using scanning electron microscopy (SEM) and spectroscopic (diffuse reflectance (DR) and infrared (IR)) techniques were examined in laboratory bioreactors with time. For both materials, there were no differences observed in the ultraviolet (UV) region among the reactors and several peaks were observed with fluctuating intensities and without any trends. For light density polyethylene (LDPE), peaks indicating the presence of biofilm could be observed in the visible region for activated sludge bioreactor, and for polyethylene terephthalate (PET), freshwater algae biofilm was also visible. PET in freshwater bioreactor is the most densely populated sample both under the optical microscope and SEM. Based on the DR spectra, different visible peaks for LDPE and PET were observed but, in both cases, the visible region peaks (~ 450 and 670 nm) correspond to the peaks found in the water samples of the bioreactors. The difference on these surfaces could not be identified with IR but the fluctuations observed in the UV wavelength region were also detectable using indices obtained from the IR spectra such as keto, ester, and vinyl. For instance, the virgin PET sample shows higher values in all the indices than the virgin LDPE sample [(virgin LDPE: ester Index (I) = 0.051, keto I = 0.039, vinyl I = 0.067), (virgin PET: ester I = 3.5, keto I = 19, vinyl I = 0.18)]. This suggests that virgin PET surface is hydrophilic as expected. At the same time, for all the LDPE samples, all the indices demonstrated higher values (especially for R2) than the virgin LDPE. On the other hand, ester and keto indices for PET samples demonstrated lower values than virgin PET. In addition, DRS technique was able to identify the formation of the biofilm both on wet and dry samples. Both DRS and IR can describe changes in the hydrophobicity during the initial formation of biofilm but DRS can better describe the fluctuations of biofilm in the visible spectra region.

Extruded polystyrene microplastics as a source of brominated flame retardant additives in the marine environment: long-term field and laboratory experiments.

Microplastics (MPs) in the environment have become a global concern, not only for the physical effects of the plastic particles themselves but also for being vectors of chemical additives. In this context, little is known about the ability of MPs, particularly extruded polystyrene microplastics (XPS-MPs), to release organic chemical additives in the marine environment. In this study, a series of field and laboratory experiments were carried out to determine the leaching behaviour of organic additives including brominated flame retardants from XPS-MPs into seawater. The conducted experiments confirmed a rapid release of bisphenol A (BPA), 2,4,6-tribromophenol (TBP), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane diastereoisomers (α-, ß-, and γ-HBCDD) from the studied MPs followed by a slower rate of release over time. The effects of environmental factors on the leaching rates of these additives were also examined. Increasing Dissolved Organic Matter (DOM) concentrations and the temperature of the seawater enhanced the release of additives by increasing their solubility and polymer flexibility. In contrast, pH tested at 7, 7.5 and 8 was found to have a minor effect on additives leaching; and salinity negatively affected the leaching rate likely due to their reduced solubility and reduced diffusion from the MPs. The present study provides empirical evidence of the behaviour of XPS-MPs as a source of organic additives in the marine environment that merit further investigation.

Valorisation of agricultural waste derived biochars in aquaculture to remove organic micropollutants from water - experimental study and molecular dynamics simulations.

In this work, we evaluated the valorisation of agricultural waste materials by transforming coconut husks and shells, corncobs and rice straw into biochar for water treatment in aquaculture. We compared the biochars' suitability for removal of organic micropollutants (acetaminophen, oxytetracycline, tetracycline, enrofloxacin, atrazine, diuron and diclofenac) from surface water needed for aquaculture. The biochars were prepared by three methods ranging from inexpensive drum kilns (200 °C) to pyrolysis with biogasfication (350-750 °C). Overall, antibiotics tetracycline and enrofloxacin were the most strongly sorbed micropollutants, and coconut husk biochar prepared at 750 °C was the best sorbent material. Molecular Dynamics simulations indicated that the major sorption mechanism is via π-π stacking interactions and there is a possibility of multilayer sorption for some of the micropollutants. We observed, a strong impact of ionic strength (salinity), which is an important consideration in coastal aquaculture applications. High salinity decreased the sorption for antibiotics oxytetracycline, tetracycline and enrofloxacin but increased diclofenac, atrazine and diuron sorption. We considered coconut husk biochar produced in drum kilns the most practical option for biochar applications in small-scale coastal aquacultures in South Asia. Pilot trials of canal water filtration at an aquaculture farm revealed that micropollutant sorption by coconut husk biochar under real-world conditions might be 10-500 times less than observed in the laboratory studies. Even so, biochar amendment of sand enhanced the micropollutant retention, which may facilitate subsequent biodegradation and improve the quality of brackish surface water used for food production in coastal aquaculture.

Physicochemical and Toxicological Assay of Leachate from Malt Spent Rootlets Biochar.

The aim of this study was to characterize the leachate derived from biochar produced from malt spent rootlets (MSR) and to evaluate the required washing level in order to provide water free from inorganic substances. MSR biochar was placed in a column and subjected to six serial washes with distilled water, and the leachate was analysed for main anions and heavy metals. The 1st wash aliquot contained increased levels of mainly phosphates (980 mg/L) and chlorides (760 mg/L), and lower levels of nitrates, sulfates, fluoride and bromide, which were decreased over washes. Zero concentrations were observed after three washes for most anions. The increased levels of Zn, Be, Cs, Mn, V and Se determined in the 1st wash aliquot were eliminated in the successive washes. The toxic potency of each wash aliquot, determined by the use of the fairy shrimp Thamnocephalus platyurus showed that the 1st and 2nd MSR biochar leachates were toxic with 4.52 and 1.46 toxic units (TU), respectively, followed by a significant elimination of toxicity after further washes.

Using diffuse reflectance spectroscopy (DRS) technique for studying biofilm formation on LDPE and PET surfaces: laboratory and field experiments.

Biofilm formation on plastic debris needs to be further investigated, because microorganisms attached to plastics are transferred in all three dimensions to new regions by ocean currents. The current study aims to investigate biofilm formation on plastic strips in aquatic ecosystems using a simple physicochemical method commonly used to characterize solid surfaces, namely, the diffuse reflectance UV-Vis spectroscopy (DRS) method. Using virgin polymers that have not being exposed to the environment as a reference, DRS peaks can be attributed to the microorganisms attached to the polymer surface with time. The polymers tested were low-density polyethylene (LDPE) and polyethylene terephthalate (PET). For LDPE strips for all sampling times in the field, the development of the peaks among 10 similar samples was rather uniform in terms of peak wavelength with time. For PET strips during the early sampling time, the development of the peaks among 10 similar samples was rather uniform in terms of peak wavelength but varied in terms of intensity. This last observation phased out with longer exposure times that the peaks had similar distribution in terms of peak wavelength and intensity. Similar experiments were run for longer exposure times both in an oligotrophic laboratory bioreactor and in the marine environment. In both cases, the biofilm on PET samples seems to reach a steady state faster than LDPE with similar peaks found on both samples DRS proved to be a robust and useful tool to study the formation of biofilm on plastic samples without any pretreatment and without sample destruction. Graphical abstract.

Application of nuclear techniques to environmental plastics research.

Plastic pollution is ubiquitous in aquatic environments and its potential impacts to wildlife and humans present a growing global concern. Despite recent efforts in understanding environmental impacts associated with plastic pollution, considerable uncertainties still exist regarding the true risks of nano- and micro-sized plastics (<5 mm). The challenges faced in this field largely relate to the methodological and analytical limitations associated with studying plastic debris at low (environmentally relevant) concentrations. The present paper highlights how radiotracing techniques that are commonly applied to trace the fate and behaviour of chemicals and particles in various systems, can contribute towards addressing several important and outstanding questions in environmental plastic pollution research. Specifically, we discuss the use of radiolabeled microplastics and/or chemicals for 1) determining sorption/desorption kinetics of a range of contaminants to different types of plastics under varying conditions, 2) understanding the influence of microplastics on contaminant and nutrient bioaccumulation in aquatic organisms, and 3) assessing biokinetics, biodistribution, trophic transfer and potential biological impacts of microplastic at realistic concentrations. Radiotracer techniques are uniquely suited for this research because of their sensitivity, accuracy and capacity to measure relevant parameters over time. Obtaining precise and timely information on the fate of plastic particles and co-contaminants in wildlife has widespread applications towards effective monitoring programmes and environmental management strategies.

Surface properties of beached plastics.

Studying plastic characteristics in the marine environment is important to better understand interaction between plastics and the environment. In the present study, high-density polyethylene (HDPE), polyethylene terephalate (PET), and polyvinyl chloride (PVC) samples were collected from the coastal environment in order to study their surface properties. Surface properties such as surface functional groups, surface topography, point of zero charge, and color change are important factors that change during degradation. Eroded HDPE demonstrated an altered surface topography and color and new functional groups. Eroded PET surface was uneven, yellow, and occasionally, colonized by microbes. A decrease in Fourier transform infrared (FTIR) peaks was observed for eroded PET suggesting that degradation had occurred. For eroded PVC, its surface became more lamellar and a new FTIR peak was observed. These surface properties were obtained due to degradation and could be used to explain the interaction between plastics, microbes, and pollutants.

Magnetite impregnation effects on the sorbent properties of activated carbons and biochars.

This paper discusses the sorbent properties of magnetic activated carbons and biochars produced by wet impregnation with iron oxides. The sorbents had magnetic susceptibilities consistent with theoretical predictions for carbon-magnetite composites. The high BET surface areas of the activated carbons were preserved in the synthesis, and enhanced for one low surface area biochar by dissolving carbonates. Magnetization decreased the point of zero charge. Organic compound sorption correlated strongly with BET surface areas for the pristine and magnetized materials, while metal cation sorption did not show such a correlation. Strong sorption of the hydrophobic organic contaminant phenanthrene to the activated carbon or biochar surfaces was maintained following magnetite impregnation, while phenol sorption was diminished, probably due to enhanced carbon oxidation. Copper, zinc and lead sorption to the activated carbons and biochars was unchanged or slightly enhanced by the magnetization, and iron oxides also contributed to the composite metal sorption capacity. While a magnetic biochar with 219 ± 3.7 m(2)/g surface area nearly reached the very strong organic pollutant binding capacity of the two magnetic activated carbons, a magnetic biochar with 68 ± 2.8 m(2)/g surface area was the best metal sorbent. Magnetic biochars thus hold promise as more sustainable alternatives to coal-derived magnetic activated carbons.

A critical evaluation of magnetic activated carbon's potential for the remediation of sediment impacted by polycyclic aromatic hydrocarbons.

Addition of activated carbon (AC) or biochar (BC) to sediment to reduce the chemical and biological availability of organic contaminants is a promising in-situ remediation technology. But concerns about leaving the adsorbed pollutants in place motivate research into sorbent recovery methods. This study explores the use of magnetic sorbents. A coal-based magnetic activated carbon (MAC) was identified as the strongest of four AC and BC derived magnetic sorbents for polycyclic aromatic hydrocarbons (PAHs) remediation. An 8.1% MAC amendment (w/w, equal to 5% AC content) was found to be as effective as 5% (w/w) pristine AC in reducing aqueous PAHs within three months by 98%. MAC recovery from sediment after three months was 77%, and incomplete MAC recovery had both, positive and negative effects. A slight rebound of aqueous PAH concentrations was observed following the MAC recovery, but aqueous PAH concentrations then dropped again after six months, likely due to the presence of the 23% unrecovered MAC. On the other hand, the 77% recovery of the 8.1% MAC dose was insufficient to reduce ecotoxic effects of fine grained AC or MAC amendment on the egestion rate, growth and reproduction of the AC sensitive species Lumbriculus variegatus.

Levels and fate of perfluoroalkyl substances in beached plastic pellets and sediments collected from Greece.

Plastic debris damages marine wildlife and ecosystems becoming an important source of marine pollution. In addition, they can sorb, concentrate and stabilise contaminants acting as toxic carriers to the marine food web. In this context, the presence of 18 perfluoroalkyl substances (PFASs) in plastic pellets (n=5) and beach sediment (n=9) samples widely distributed around Greek coastal areas was assessed. The results, mainly, showed the sorption of PFASs onto pellet surface from surrounding water with concentrations from method limit of quantification to 115 ng/kg for C5, C7, C8 and C10 carboxylic acids and C8 sulfonate acid. A similar pattern was found by comparing plastic pellets and sediment for the same sampling locations that could indicate a common origin of contamination in both types of samples. However, since the number of analysed samples is limited, a more comprehensive study with a higher number of samples should be performed in future research.

Alcohol and dilution water characteristics in distilled anis (ouzo).

The authenticity of some mixed drinks such as vodka or rum was correlated to the conductivity of the dilution water. Authentic drinks demonstrated low conductivity, suggesting the use of treated water, whereas fraud drinks were mixed with regular tap water. The objective of the present study was to test if this criterion is valid for distilled anis, also known as ouzo. Several Greek distilled anis samples, mostly ouzo samples, were tested for different parameters including conductivity, pH, and percentage of different alcohol constituents. Because ouzo in Greece is commonly produced by small enterprises, no correlation between conductivity and the size of the producer was possible. Neither was it possible to correlate the price or high consumption with conductivity and, thus, prior water treatment. Alcohol quality in terms of undesirable constituents, such as methanol content, was good and comparable among samples. In ouzo, water is related to the producer quality goal for the final product and, thus, it is treated and used accordingly.

Aqueous phenanthrene toxicity after high-frequency ultrasound degradation.

Given that polycyclic aromatic hydrocarbons (PAHs), such as phenanthrene (PH), possess a potent risk for aquatic biota, a great attempt to develop and apply advanced oxidation processes, such as ultrasound (US), is of great concern nowadays. However, because US PAH-derived toxic intermediates are difficult to detect, the present study investigates aqueous PH toxicity before and after high-frequency US degradation, in hemocytes of mussel Mytilus galloprovincialis. Specifically, cell viability (with the use of neutral red uptake/NRU method), and oxidative-stress indices in terms of superoxide anions, (O2(-)), nitric oxides (NO, in terms of nitrites), lipid peroxidation products (in terms of malondialdehyde/MDA content) and DNA damage (with the use of Comet assay method) were investigated in mussel hemocytes exposed to environmentally relevant concentrations of PH (0.01, 0.1, 1 and 10 µg L(-1)), before and after US treatment for 120 min (at a frequency of 582 kHz). According to the results, the NRU method showed a significant attenuation of PH-induced mortality in US PH-treated hemocytes in all cases. Moreover, the increased levels of O2(-) and NO generation, as well as MDA content measured in PH-treated hemocytes, were drastically decreased after US degradation in any case. Similarly, the disturbance of DNA integrity (in terms of % DNA in tail, OM and TM), was negligible in case of US PH-treated hemocytes. Although further in vitro and in vivo studies are needed, the present study showed for the first time that high frequency US could be applied as a highly efficient and "environmentally friendly" process for degrading low molecular weight PAH, such as PH.

Phenanthrene removal from aqueous solutions using well-characterized, raw, chemically treated, and charred malt spent rootlets, a food industry by-product.

Malt spent rootlets (MSR) are biomaterials produced in big quantities by beer industry as by-products. A sustainable solution is required for their management. In the present study, MSR are examined as sorbents of a hydrophobic organic compound, phenanthrene, from aqueous solutions. Raw MSR sorb phenanthrene but their sorptive properties are not competitive with the respective properties of commercial sorbents (e.g., activated carbons). Organic petrography is used as a tool to characterize MSR after treatment in order to produce an effective sorbent for phenanthrene. Chemical and thermal (at low temperature under nitrogen atmosphere) treatments of MSR did not result in highly effective sorbents. Based on organic petrography characterization, the pores of the treated materials were filled with humic colloids. When pyrolysis at 800 °C was used to treat MSR, a sorbent with new and empty pores was produced. Phenanthrene sorption capacity was 2 orders of magnitude higher for the pyrolized MSR than for raw MSR.

Responses of Lumbriculus variegatus to activated carbon amendments in uncontaminated sediments.

Activated carbon (AC) amendment is a recently developed sediment remediation method. The strong hydrophobic organic contaminant sorption efficiency of AC has been shown in several studies, but effects on benthic organisms require more investigation. The AC induced effects on egestion rate, growth and reproduction of Lumbriculus variegatus were studied by applying bituminous coal based AC in three different particle size fractions, namely <63 µm (90%, AC(p)), 63-200 µm (AC(m)) and 1000 µm (AC(g)), to natural uncontaminated (HS) and artificial sediment (AS). Egestion rate, growth and reproduction decreased with increasing AC concentration and finer AC particle fractions, effects being stronger on HS than on AS sediment. Lipid content in AS was reduced already at the lowest AC doses applied (AC(p) and AC(m) 0.05%, AC(g) 0.25%). In addition, hormesis-like response was observed in growth (AS) and reproduction (AS, HS) indicating that AC may disturb organisms even at very low doses. Potential ecological effects need to be further evaluated in an amendment- and site-specific manner.

Surface properties of beached plastic pellets.

The presence of pollutants on plastic debris is an emerging environmental hot topic. Understanding the surface alteration of plastics while in the marine environment increases our understanding of the pollutant-plastic debris interaction. Plastic pellets are widely distributed throughout the world oceans. Eroded and virgin polyethylene (PE) and polypropylene (PP) pellets were studied for their surface properties to better understand the interaction between plastic and compounds in marine environment. Surface properties such as point of zero charge, surface area and pore volume, surface topography, functional groups and acid-base behavior are important factors which affect sorption. Virgin plastic pellets had homogeneous smooth surfaces that do not have any acid-base behavior. Eroded PE demonstrates an altered surface that at seawater pH acquires a negative charge due to ketone groups. The uneven surface and possible functional groups could have been formed from the erosion processes while floating at the sea surface and might explain the interaction of eroded plastics with microbes and metals.

Assessing the effect of grain-scale sorption rate limitations on the fate of hydrophobic organic groundwater pollutants.

Subsurface pollutant transport models accounting for sorption rate limitations are computationally more demanding than those assuming local sorption equilibrium. We combine batch and column tests with modeling for a comparative assessment of different sorption models. For the relatively hydrophobic compound naphthalene, a model assuming local sorption equilibrium was unable to reproduce breakthrough curves in column studies with Canadian River Alluvium sediment which contains carbonaceous particles. Fully calibrated independent forward predictions of a first-order kinetic and two diffusion kinetic sorption models were in much better agreement with the experimental data. Predictions using a diffusion-limited kinetic sorption model assuming concentration-independent sorption coefficients performed equally well as a model using the Freundlich isotherm. Both diffusion-based kinetic sorption models were superior to the first-order rate approach. In the present study, the validity of the local sorption equilibrium assumption is discussed based on a Damköhler number and thus, the compound's sorption properties, the aquifer properties, and the scale of the process. Relatively high groundwater velocities in combination with a low sorption coefficient K(d) and slow diffusion limited sorption kinetic rates are necessary conditions to justify the implementation of grain-scale sorption rate limitations in groundwater contaminant fate models. Such conditions exist when a low amount of carbonaceous particles is present in aquifers with high permeability.