The increasing use of artificial light at night (ALAN) has led to exposure of freshwater ecosystems to light pollution worldwide. Simultaneously, the spectral composition of nocturnal illumination is changing, following the current shift in outdoor lighting technologies from traditional light sources to light emitting diodes (LED). LEDs emit broad-spectrum white light, with a significant amount of photosynthetically active radiation, and typically a high content of blue light that regulates circadian rhythms in many organisms. While effects of the shift to LED have been investigated in nocturnal animals, its impact on primary producers is unknown. We performed three field experiments in a lowland agricultural drainage ditch to assess the impacts of a transition from high-pressure sodium (HPS) to white LED illumination (color temperature 4000 K) on primary producers in periphyton. In all experiments, we compared biomass and pigment composition of periphyton grown under a natural light regime to that of periphyton exposed to nocturnal HPS or, consecutively, LED light of intensities commonly found in urban waters (approximately 20 lux). Periphyton was collected in time series (1–13 weeks). We found no effect of HPS light on periphyton biomass; however, following a shift to LED the biomass decreased up to 62%. Neither light source had a substantial effect on pigment composition. The contrasting effects of the two light sources on biomass may be explained by differences in their spectral composition, and in particular the blue content. Our results suggest that spectral composition of the light source plays a role in determining the impacts of ALAN on periphyton and that the ongoing transition to LED may increase the ecological impacts of artificial lighting on aquatic primary producers. Reduced biomass in the base of the food web can impact ecosystem functions such as productivity and food supply for higher trophic levels in nocturnally-lit ecosystems.

Male fertility is progressively declining in many developed countries, but the relationship between male infertility and environmental factors is still unclear.To assess the influence of environmental temperature and air pollution on semen parameters, using a big-data approach.A big data analysis of parameters related to 5131 men, living in a province of Northern Italy and undergoing semen analyses between January 2010 and March 2016 was performed. Ambient temperature was recorded on the day of analysis and the 90 days prior to the analysis and the average value of particulate matter (PM) and NO2 in the year of the test. All data were acquired by geocoding patients residential address. A data warehouse containing 990,904,591 data was generated and analysed by multiple regressions.5573 semen analyses were collected. Both maximum and minimum temperatures registered on the day of collection were inversely related to total sperm number (p < .001), non-progressive motility (NPrM) (p < .005) and normal forms (p < .001). Results were confirmed considering temperature in the 30 and 60 days before collection, but not in the 90 days before collection. Total sperm number was lower in summer/autumn (p < .001) and was inversely related with daylight duration (p < .001). PM10 and PM2.5 were inversely related to PrM (p < .001 and p < .005) and abnormal forms (p < .001).This is the first evaluation of the relationship between male fertility-related parameters and environment using a big-data approach. A seasonal change in semen parameters was found, with a fluctuation related to both temperature and daylight duration. A negative correlation between air pollution and semen quality is suggested. Such seasonal and environmental associations should be considered when assessing changes of male fertility-related parameters over time.

In this work we have investigated in details the process of degradation of the 4-amino-6-chlorobenzene-1,3-disulfonamide (ABSA), stable hydrolysis product of frequently used pharmaceutical hydrochlorothiazide (HCTZ), as one of the most ubiquitous contaminants in the sewage water. The study encompassed investigation of degradation by hydrolysis, photolysis, and photocatalysis employing commercially available TiO₂ Degussa P25 catalyst. The process of direct photolysis and photocatalytic degradation were investigated under different type of lights. Detailed insights into the reactive properties of HCTZ and ABSA have been obtained by density functional theory calculations and molecular dynamics simulations. Specifically, preference of HCTZ towards hydrolysis was confirmed experimentally and explained using computational study. Results obtained in this study indicate very limited efficiency of hydrolytic and photolytic degradation in the case of ABSA, while photocatalytic degradation demonstrated great potential. Namely, after 240 min of photocatalytic degradation, 65% of ABSA was mineralizated in water/TiO₂ suspension under SSI, while the nitrogen was predominantly present as NH4+. Reaction intermediates were studied and a number of them were detected using LC-ESI-MS/MS. This study also involves toxicity assessment of HCTZ, ABSA, and their mixtures formed during the degradation processes towards mammalian cell lines (rat hepatoma, H-4-II-E, human colon adenocarcinoma, HT-29, and human fetal lung, MRC-5). Toxicity assessments showed that intermediates formed during the process of photocatalysis exerted only mild cell growth effects in selected cell lines, while direct photolysis did not affect cell growth.

Recent advances in research on algae inhibition by using low-cost straw proposed a possible mechanism that reactive oxygen species (ROS) generated by the solar irradiation of straw-derived dissolved organic matter (DOM) might contribute to cyanobacteria inhibition. However, this process is not clearly understood. Here, DOM from three types of straw (barley, rice, and wheat) and natural organic matter (NOM) isolates were investigated in terms of their photochemical properties and ROS generating abilities. Results demonstrated that the DOM derived from the aeration decomposition of barley straw (A-DOMbs) yielded the best formation efficiencies of hydrogen peroxide (H₂O₂) and hydroxyl radicals (•OH) under solar-simulated irradiation in all organic matter samples. Correlation analysis implies that optical parameters and phenolic hydroxyl group contents can signify ROS generating abilities of different DOM solutions. Bioassay results show that A-DOMbs possesses the highest inhibition performance for M. aeruginosa in all DOM samples, much higher than those of NOM isolates. The addition of catalase greatly relieves the inhibition performance, making the loss of chlorophyll a content decreased from 37.14% to 7.83% in 2 h for A-DOMbs, which implies that for cyanobacteria growth inhibition, photochemically-produced H₂O₂ from SOM is far more important than singlet oxygen (¹O₂), •OH, and even SOM itself. Our results show that H₂O₂ photochemically generated from straw-derived DOM is able to result in rapid inhibition of M. aeruginosa in a relatively short period, furthering the understanding of complicated mechanisms of cyanobacteria inhibition by using low-cost straw in eutrophic waters.

Occurrence of per- and poly-fluoroalkyl substances (PFASs) in the environment and biota has raised a great concern to public health because these compounds are persistent, bioaccumulative, and toxic. Biodegradation of polyfluoroalkyl substances, particularly long-chain fluorotelomer-based products, can lead to production of various short-chain PFASs, with 5:3 fluorotelomer carboxylic acid (referred as 5:3 FTCA hereafter) as a dominant polyfluoroalkyl metabolite. Perfluoroalkyl acids, particularly perfluorooctanoic acid (PFOA), are toxic and current removal methods are not cost-effective. This study reports the photodegradation of 5:3 FTCA and PFOA using ZnO as a photocatalyst under neutral pH and room temperature conditions. Under long UV wavelength (365 nm), both tetrapod and commercial ZnO can photodegrade 5:3 FTCA. Five removal products—perfluorohexanoic acid, perfluoropentanoic acid, perfluorobutyric acid, 5:2 fluorotelomer carboxylic acid (5:2 FTCA), and inorganic fluoride—were identified, with PFBA and F⁻ as dominant end products. SEM and XPS high-resolution scans on the surface of the utilized ZnO showed less units of CF₂ than that in 5:3 FTCA, supporting occurrence of photodegradation of 5:3 FTCA by ZnO. Defluorination of PFOA was not observed with ZnO only, but at pH 5 and in the co-presence of Fe-citrate. PFOA defluorination increased from 0.93% after 3 days of UV light exposure to 3.9% after additional 135 h under direct sunlight exposure. To the authors’ best knowledge, this is the first report studying ZnO-catalyzed photodegradation of 5:3 FTCA, and examining the Fe co-addition for PFOA defluorination.

Virgin polyvinyl chloride (PVC) particles were exposed to heat, ultraviolet B (UVB) and solar radiation either in artificial seawater or in air for different periods of time. The surface and chemical properties of fresh and degraded particle surfaces were determined via image analysis using scanning electron micrographs, a Brunauer-Emmett-Teller (BET) specific surface area analyzer and infrared spectroscopy. Thermal and UVB degradation resulted in unique PVC morphologies. In addition, the increased presences of functional groups were evident as dehydrochlorination and oxidation during the degradation process, which altered the chemical properties of PVC. In contrast, under solar exposure with or without seawater, unevenness to the surface was noted that seems to originate from degradation of the PVC surface; in addition, no new functional groups were found. This suggests that the chemical properties of PVC are stable over extended periods in the marine environment.

There is growing global concern over the chemical, biological and ecological impact of plastics in the ocean. Remote sensing has the potential to provide long-term, global monitoring but for marine plastics it is still in its early stages. Some progress has been made in hyperspectral remote sensing of marine macroplastics in the visible (VIS) to short wave infrared (SWIR) spectrum. We present a reflectance model of sunlight interacting with a sea surface littered with macro plastics, based on geometrical optics and the spectral signatures of plastic and seawater. This is a first step towards the development of a remote sensing algorithm for marine plastic using light reflectance measurements in air. Our model takes the colour, transparency, reflectivity and shape of plastic litter into account. This concept model can aid the design of laboratory, field and Earth observation measurements in the VIS-SWIR spectrum and explain the results.

Remote sensing of plastic littering natural waters is an emerging field of science with the potential to provide observations on local to global scales. We present the verification of a theoretical reflectance model of sunlight interacting with a water surface littered with buoyant plastic objects. We measured a few common litter items of different polymers as well as shapes, transparencies, and surface roughnesses. Spectral reflectance measurements in the field were backed up with measurements in the laboratory of coefficients of total and diffuse reflectance, transmittance and absorption. We evaluated a single-band algorithm for 850 nm wavelength and a dual-band algorithm using a second wavelength at a polymer absorption band between 1660 and 1730 nm. Both algorithms were plastic litter type specific. Our findings show that for interpreting spectral remote sensing of floating plastic, physical properties that control geometrical optics should complement information about the absorption spectra of the polymer.

This article describes a methodology for optimising predictive models for concentrations of faecal indicator organisms (FIOs) in coastal areas based on geographic and meteorological characteristics of upstream catchments. Concentrations of FIOs in mussels and water sampled from 50 sites in the south of Brazil from 2012 to 2013 were used to develop models to separately predict the spatial and temporal variations of FIOs. The geographical parameters used in predictive models for the spatial variation of FIOs were human population, urban area, percentage of impervious cover and total catchment area. The R2 of models representing catchments located within 3.1 km from the monitoring points was up to 150% higher than that for the nearest catchment. The temporal variation of FIOs was modelled considering the combined effect of meteorological parameters and different time windows. The explained variance in models based on rainfall and solar radiation increased up to 155% and 160%, respectively.

In this work, disks containing different amount of the TiO₂ precursor impregnated on the raw red clay were produced. The disks were obtained by pressing in metal template and subsequently calcined at 500 °C. The raw clay was used as rigid support to fix the TiO₂. The materials were characterized by X-ray diffraction, diffuse reflectance spectroscopy, N₂ adsorption-desorption (BET and BJH), scanning electron microscopy, and Fourier transform infrared (FTIR) spectroscopy. The ability of disks to produce superoxide and hydroxyl radicals after photoexcitation with UV irradiation was monitored by EPR. The catalytic efficiency was evaluated by the Reactive Red 141 dye discoloration under artificial UV light and sunlight. The reaction parameters such as concentration of RR-141 and irradiation source were evaluated. The results showed that the disks were able to decolorize 97.5% under sunlight at 60 min. The disks were also efficient in the discoloration until the tenth cycle, resulting in discoloration values near the initial cycles. Additionally, the dye fragments produced in cleavage of molecule during the reaction were evaluated by LC/MS-MS. Graphical Abstract