The behavior of photoactive TiO2 nanoparticles in an aquatic environment under UV irradiation was investigated. When there was no UV light irradiation, the attachment of humic acid (HA) onto the TiO2 nanoparticles improved their stability due to an increase in the electrostatic and steric repulsions between the particles. However, our study demonstrated that UV light clearly influenced the aggregation of TiO2 nanoparticles. Half an hour of UV irradiation caused the particles to aggregate from 331.0 nm to 1505.0 nm at a pH of 3.0. Similarly, the particles aggregated from 533.2 nm to 1037.0 nm at a pH of 6.5 and from 319.0 nm to 930.0 nm at a pH of 9.0. The aggregation continued with increased irradiation time, except for the condition at pH 3.0, which demonstrated disaggregation. Furthermore, we determined that the photocatalytic degradation of the HA dominated the behavior of TiO2 in our study. From the results of HA removal and 3DEEM fluorescence spectra data for the solution, a change in the HA was in accordance with the size change of the TiO2. The results illustrated that the UV irradiation affected the behavior of light-active nanomaterial (such as TiO2) in an aquatic system, thus influencing their bioavailability and reactivity.

Tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) is considered a re-emerging environmental pollutant, and exposure to environmentally relevant concentrations has been shown to cause individual developmental toxicity in zebrafish and the water flea (Daphnia magna). However, multigenerational effects during exposure to TDCIPP and after subsequent recovery were unknown. In the present study, individuals of a model aquatic organism, the ciliated protozoan, T. thermophila were exposed to environmentally-relevant concentrations of TDCIPP (0, 300 or 3000 ng/L) for 60 days (e.g., theoretically 372 generations) followed by a 60-day period of recovery, during which T. thermophila were not exposed to TDCIPP. During exposure and after exposure, effects at the molecular, histological, individual and population levels were examined. Multigenerational exposure to 300 or 3000 ng TDCIPP/L for 60 days significantly decreased numbers of individuals, sizes of individuals, expressed as length and width of bodies, number of cilia, and depth and diameter of basal bodies of cilia, and up-regulated expressions of genes related to assembly and maintenance of cilia. Complete or partial recoveries of theoretical sizes of populations as well as sizes of individuals and expressions of genes were observed during the 60-day recovery period. Effects on number of cilia and depth and diameter of basal body of cilia were not reversible and could still be observed long after cease of TDCIPP exposure. Collectedly, and shown for the first time, multigenerational effects to T. thermophila were caused by exposure to environmentally relevant concentrations of TDCIPP. Also, there were multi-generational effects at the population level that were not caused by carry-over exposure to TDCIPP. The “permanent” alterations and their potential significance are discussed.

The antipsychotic drug quetiapine (QUT) has been frequently detected in sewage treatment plants. However, information on the fate of QUT in aquatic environments and its behavior during UV treatment is limited. In this study, QUT is shown not to be readily biodegradable in the Closed Bottle Test and the Manometric Respirometry Test according to OECD guidelines. The main biotransformation product (BTP) formed in the tests, a carboxylic acid derivative, was identified by means of high-resolution mass spectrometry. This BTP is presumably a human metabolite and showed higher detection rates than QUT in a river sampling campaign conducted in northern Germany. UV elimination kinetics of QUT at different initial concentrations (226.5, 45.3, 11.3, and 2.3 μmol L−1) were faster at lower initial concentrations. All seven phototransformation products (PTPs) could be still identified at initial concentration of 11.3 μmol L−1. The photolytic mixture generated after 128 min of photolysis of QUT was not better biodegradable than QUT. Initial UV treatment of QUT led to the formation of several additional BTPs. Four of them were identified. The bacterial cytotoxicity and genotoxicity before and after phototransformation of QUT in a modified luminescent bacteria test (LBT) and the umu-test (ISO/FDIS 13829) showed cytotoxic effects in the LBT for QUT. Furthermore, PTPs had similar cytotoxic effects on luminescent bacteria. The umu-test did not reveal any genotoxic activity for QUT or PTPs. In conclusion, the release of QUT into sewage treatment plants and aquatic environments could result in the formation of a main BTP. Additional UV treatment of QUT would lead to the formation of additional BTPs. Moreover, treatment did not result in lower toxicity to tested organisms. In conclusion, UV treatment of QUT should be considered critically as a potential treatment for QUT in aquatic systems.

Plastics are common and pervasive anthropogenic debris in marine environments. Floating plastics provide opportunities to alter the abundance, distribution and invasion potential of sessile organisms that colonize them. We selected plastics from seven recycle categories and quantified settlement of (i) bryozoans Bugula neritina (Linnaeus, 1758) in the lab and in the field, and of (ii) barnacles Amphibalanus (= Balanus) amphitrite (Darwin, 1854) in the field. In the laboratory we cultured barnacles on the plastics for 8 weeks and quantified growth, mortality, and breaking strength of the side plates. In the field all recyclable plastics were settlement substrata for bryozoans and barnacles. Settlement depended on the type of plastic. Fewer barnacles settled on plastic surfaces compared to glass. In the lab and in the field, bryozoan settlement was higher on plastics than on glass. In static laboratory rearing, barnacles growing on plastics were initially significantly smaller than on glass. This suggested juvenile barnacles were adversely impacted by materials leaching from the plastics. Barnacle mortality was not significantly different between plastic and glass surfaces, but breaking strength of side plates of barnacles on polyvinyl chloride (PVC) and polycarbonate (PC) were significantly lower than breakage strength on glass. Plastics impact marine ecosystems directly by providing new surfaces for colonization with fouling organisms and by contaminants shown previously to leach out of plastics and impact biological processes.

We investigated how the adaptation to metalliferous environments can influence the plant response to biotic stress. In a metallicolous and a non-metallicolous population of Silene paradoxa the induction of oxidative stress and the production of callose and volatiles were evaluated in the presence of copper and of the PAMP fungal protein cerato-platanin, separately and in combination. Our results showed incompatibility between the ordinary ROS-mediated response to fungal attack and the acquired mechanisms of preventing oxidative stress in the tolerant population. A similar situation was also demonstrated by the sensitive population growing in the presence of copper but, in this case, with a lack of certain responses, such as callose production. In addition, in terms of the joint behaviour of emitted volatiles, multivariate statistics showed that not only did the populations respond differently to the presence of copper or biotic stress, but also that the biotic and abiotic stresses interacted in different ways in the two populations.Our results demonstrated that the same incompatibility of hyperaccumulators in ROS-mediated biotic stress signals also seemed to be exhibited by the excluder metallophyte, but without the advantage of being able to rely on the elemental defence for plant protection from natural enemies.

The Antarctic continent is among the most pristine regions; yet various organic contaminants have been measured there routinely. Air and snow samples were collected during the austral spring (October–November, 2010) along the western Antarctic Peninsula and analyzed for organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) to assess the relative importance of long-range transport versus local primary or secondary emissions. Highest concentrations of PCBs, PBDEs and DDTs were observed in the glacier’s snow sample, highlighting the importance of melting glaciers as a possible secondary source of legacy pollutants to the Antarctic. In the atmosphere, contaminants were mainly found in the vapor phase (>65%). Hexachlorobenzene (33.6 pg/m3), PCBs (11.6 pg/m3), heptachlor (5.64 pg/m3), PBDEs (4.22 pg/m3) and cis-chlordane (2.43 pg/m3) were the most abundant contaminants. In contrast to other compounds, PBDEs seem to have originated from local sources, possibly the research station itself. Gas-particle partitioning for analytes were better predicted using the adsorption partitioning model than an octanol-based absorption approach. Diffusive flux calculations indicated that net deposition is the dominant pathway for PBDEs and chlordanes, whereas re-volatilization from snow (during melting or metamorphosis) was observed for PCBs and some OCPs.

Ambient fine particulate matter samples were collected during 2009–2013 in Chengdu, a megacity in western China, and the samples were speciated into organic carbon (OC), elemental carbon (EC), char-EC, soot-EC, eight carbon fractions, inorganic elements and water-soluble ions. Char-EC and soot-EC contribute to the better understanding of the sources and properties of EC. The highest levels of most carbon fractions were found in winter and May. The higher OC/EC ratio in winter suggests higher SOC fraction in winter, and higher char-EC/soot-EC ratio in May are the direct consequences of straw burning activities. Source contributions to PM2.5 and carbonaceous aerosols were quantified using the ME2 receptor model. Major contributors to OC in PM2.5 are vehicular exhaust (36.5%), coal combustion & straw burning (35.2%) and SOC (27.0%). The first two categories also contributed 51.4% and 49.3% of char-EC in PM2.5. Vehicular exhaust dominated soot-EC, contributing 63.0% to soot-EC in PM2.5. SOC contributed to high OC levels in winter due to the increase of precursor emissions and stable meteorological conditions. Coal combustion & straw burning show higher contributions to OC, char-EC and soot-EC in winter months and in May, which can be explained, in part, by increased coal consumption in winter and straw burning activities in May. Vehicular exhaust contributions are not strongly associated with monthly nor weekday-weekend patterns, resulting in that soot-EC vary insignificantly by month nor by weekday.

Pyrethroids and metals were simultaneously detected in aquatic environment and showed antagonistic lethality to the benthic invertebrate, Chironomus dilutus. Accelerated biotransformation of pyrethroids in organism by the presence of metals was proposed as the likely reason for the antagonism. Mechanistic explanation for the role of toxicokinetics of pyrethroids in the antagonistic interaction would help better understanding the reasons for the joint toxicity. The goal was achieved in the current study by evaluating the impact of cadmium on toxicokinetic parameters of permethrin in C. dilutus, and by explaining the interaction through quantifying the activity and gene expression of biotransformation-related enzymes. Toxicokinetic parameters were simulated using a first-order kinetic model. Bioconcentration factors and uptake and elimination rate constants for permethrin were not significantly changed with the addition of cadmium at sublethal level, neither did the activity of enzymes, including glutathione S-transferase (GST), carboxylesterase (CarE), catalase and lipid peroxidation. Yet, the activities of metabolism-related enzymes (GST and CarE) showed an elevating tendency with adding cadmium. Furthermore, the expression of metabolism-related genes, including cytochrome P450 and glutathione S-transferase genes were significantly up-regulated in C. dilutus exposed to a mixture of permethrin and cadmium compared with permethrin only. Although co-exposure to cadmium did not induce toxicokinetic changes of permethrin in C. dilutus, it did enhance the activity of metabolic enzymes which were encoded by the metabolism-related genes, suggesting an acceleration of biotransformation of permethrin to less toxic metabolites in the midges. This possibly explained the antagonistic interaction for permethrin and cadmium.

Iron reduction is one of the important organic matter (OM) mineralization pathway in sediments. Here we investigated the rates and the relative contribution of iron reduction to OM mineralization in Zhushan bay (ZSB, cyanobacterial bloom biomass (CBB)-dominated habitats) and East Taihu Lake (ETL, submerged macrophypes (SM)-dominated habitats) of Lake Taihu, China. Anaerobic microcosm incubation revealed that the rate of iron reduction at ZSB (4.42 μmol cm−3 d−1) in summer was almost 1.5 times higher than at ETL (3.13 μmol cm−3 d−1). Iron reduction accounted for 66.5% (ZSB) and 31.8% (ETL) of total anaerobic carbon mineralization, respectively. No detectable methanogenesis was found at ZSB, while methanogenesis was responsible for 16.7% of total anaerobic respiration in sediments of ETL. Geochemical analysis of solid phase constituents indicated that ZSB surface sediments experienced highly oxidizing conditions with much higher amorphous Fe(III) (71 mmol m−2) than ETL (11 mmol m−2). Conversely, AVS inventories at ETL (38 mmol m−2) were up to 30 times higher than at ZSB (1.27 mmol m−2), indicating significant sulfate reduction in sediments of ETL. Overall results suggested that varying carbon sources and distinct geochemical characterizations of the sediments in contrasting habitats significantly influenced the rate of iron reduction and the pathway of C mineralization in a large freshwater lake.

Passive sampling devices (PS) are widely used for pollutant monitoring in water, but estimation of measurement uncertainties by PS has seldom been undertaken. The aim of this work was to identify key parameters governing PS measurements of metals and their dispersion. We report the results of an in situ intercomparison exercise on diffusive gradient in thin films (DGT) in surface waters. Interlaboratory uncertainties of time-weighted average (TWA) concentrations were satisfactory (from 28% to 112%) given the number of participating laboratories (10) and ultra-trace metal concentrations involved. Data dispersion of TWA concentrations was mainly explained by uncertainties generated during DGT handling and analytical procedure steps. We highlight that DGT handling is critical for metals such as Cd, Cr and Zn, implying that DGT assembly/dismantling should be performed in very clean conditions. Using a unique dataset, we demonstrated that DGT markedly lowered the LOQ in comparison to spot sampling and stressed the need for accurate data calculation.