We investigated isoprene (ISO) emission and gas exchange in leaves from different positions along the vertical canopy profile of poplar saplings (Populus euramericana cv. ‘74/76’). For a growing season, plants were subjected to four N treatments, control (NC, no N addition), low N (LN, 50 kg N ha⁻¹year⁻¹), middle N (MN, 100 kg N ha⁻¹year⁻¹), high N (HN, 200 kg N ha⁻¹year⁻¹) and three O₃ treatments (CF, charcoal-filtered ambient air; NF, non-filtered ambient air; NF + O₃, NF + 40 ppb O₃). Our results showed the effects of O₃ and/or N on standardized ISO rate (ISOᵣₐₜₑ) and photosynthetic parameters differed along with the leaf position, with larger negative effects of O₃ and positive effects of N on ISOᵣₐₜₑ and photosynthetic parameters in the older leaves. Expanded young leaves were insensitive to both treatments even at very high O₃ concentration (67 ppb as 10-h average) and HN treatment. Significant O₃ × N interactions were only found in middle and lower leaves, where ISOᵣₐₜₑ declined by O₃ just when N was limited (NC and LN). With increasing light-saturated photosynthesis and chlorophyll content, ISOᵣₐₜₑ was reduced in the upper leaves but on the contrary increased in middle and lower leaves. The responses of ISOᵣₐₜₑ to AOT40 (accumulated exposure to hourly O₃ concentrations > 40 ppb) and PODY (accumulative stomatal uptake of O₃ > Y nmol O₃ m⁻² PLA s⁻¹) were not significant in upper leaves, but ISOᵣₐₜₑ significantly decreased with increasing AOT40 or PODY under limited N supply in middle leaves but at all N levels in lower leaves. Overall, ISOᵣₐₜₑ changed along the vertical canopy profile in response to combined O₃ and N exposure, a behavior that should be incorporated into multi-layer canopy models. Our results are relevant for modelling regional isoprene emissions under current and future O₃ pollution and N deposition scenarios.

Sea-spray (or sea-salt) aerosol (SSA) formation and their subsequent atmospheric transport and deposition have been suggested to play a prominent role in the occurrence of ionizable perfluoroalkyl substances (PFAS) in the maritime Antarctica and other remote regions. However, field studies on SSA’s role as vector of transport of PFAS are lacking. Following a multiphase approach, seawater (SW), the sea-surface microlayer (SML) and SSA were sampled simultaneously at South Bay (Livingston Island, Antarctica). Average PFAS concentrations were 313 pg L⁻¹, 447 pg L⁻¹, and 0.67 pg m⁻³ in SW, the SML and SSA, respectively. The enrichment factors of PFAS in the SML and SSA ranged between 1.2 and 5, and between 522 and 4690, respectively. This amplification of concentrations in the SML is consistent with the surfactant properties of PFAS, while the large enrichment of PFAS in atmospheric SSA may be facilitated by the large surface area of SSA and the sorption of PFAS to aerosol organic matter. This is the first field work assessing the simultaneous occurrence of PFAS in SW, the SML and SSA. The large measured amplification of concentrations in marine aerosols supports the role of SSA as a relevant vector for long-range atmospheric transport of PFAS.

The bioaccessibility of arsenic and its speciation are two important factors in assessing human health risks exposure to contaminated soils. However, the effects of human gut microbiota on arsenic bioaccessibility and its speciation are not well characterized. In this study, an improved in vitro model was utilized to investigate the bioaccessibility of arsenic in the digestive tract and the role of human gut microbiota in the regulation of arsenic speciation. For all soils, arsenic bioaccessibility from the combined in vitro model showed that it was <40% in the gastric, small intestinal and colon phases. This finding demonstrated that the common bioaccessibility approach assuming 100% bioaccessibility would overestimate the human health risks posed by contaminated soils. Further to this, the study showed that arsenic bioaccessibility was 22% higher in the active colon phase than that in the sterile colon phase indicating that human colon microorganisms could induce arsenic release from the solid phase. Only inorganic arsenic was detected in the gastric and small intestinal phases, with arsenate [As(V)] being the dominant arsenic species (74%–87% of total arsenic). Arsenic speciation was significantly altered by the active colon microbiota, which resulted in the formation of methylated arsenic species, including monomethylarsonic acid [MMA(V)] and dimethylarsinic acid [DMA(V)] with low toxicity, and a highly toxic arsenic species monomethylarsonous acid [MMA(III)]. Additionally, a high level of monomethylmonothioarsonic acid [MMMTA(V)] (up to 17% of total arsenic in the extraction solution) with unknown toxicological properties was also detected in the active colon phase. The formation of various organic arsenic species demonstrated that human colon microorganisms could actively metabolize inorganic arsenic into methylated arsenicals and methylated thioarsenicals. Such transformation should be considered when assessing the human health risks associated with oral exposure to soil.

Fish farming in coastal areas has become an important source of food to support the world’s increasing population. However, intensive and unregulated mariculture activities have contributed to changing seawater carbonate chemistry through the production of high levels of respiratory CO₂. This additional CO₂, i.e. in addition to atmospheric inputs, intensifies the effects of global ocean acidification resulting in localized extreme low pH levels. Marine calcifying macroalgae are susceptible to such changes due to their CaCO₃ skeleton. Their physiological response to CO₂-driven acidification is dependent on their carbon physiology. In this study, we used the pH drift experiment to determine the capability of 9 calcifying macroalgae to use one or more inorganic carbon (Cᵢ) species. From the 9 species, we selected the rhodolith Sporolithon sp. as a model organism to investigate the long-term effects of extreme low pH on the physiology and biochemistry of calcifying macroalgae. Samples were incubated under two pH treatments (pH 7.9 = ambient and pH 7.5 = extreme acidification) in a temperature-controlled (26 ± 0.02 °C) room provided with saturating light intensity (98.3 ± 2.50 μmol photons m⁻² s⁻¹). After the experimental treatment period (40 d), growth rate, calcification rate, nutrient uptake rate, organic content, skeletal CO₃⁻², pigments, and tissue C, N and P of Sporolithon samples were compared. The pH drift experiment revealed species-specific Cᵢ use mechanisms, even between congenerics, among tropical calcifying macroalgae. Furthermore, long-term extreme low pH significantly reduced the growth rate, calcification rate and skeletal CO₃⁻² content by 79%, 66% and 18%, respectively. On the other hand, nutrient uptake rates, organic matter, pigments and tissue C, N and P were not affected by the low pH treatments. Our results suggest that the rhodolith Sporolithon sp. is susceptible to the negative effects of extreme low pH resulting from intensive mariculture-driven coastal acidification.

The current air pollution by SO₂ due to anthropogenic pressure in Poland was assessed based on sulfur concentrations in pine needles (Pinus sylvestris L.). On 308 monitoring sample plots located in pine stands distributed across Poland, measurements were conducted in mineral soil layers (0–10 cm, 10–40 cm, 40–100 cm) and in the soil organic layer (+5–0 cm). Samples of Scots pine foliage (current-year needles) were then collected, and the sulfur concentration in these needles was determined. Based on these data, a map of the spatial variability of sulfur concentrations in pine needles was drawn. The mean sulfur concentration in the pine needles was 854.8 mg kg⁻¹ in dry mass. Higher SO₂ emissions were noted in regions influenced by industry, such as the Upper Silesia and regions under strong urban pressure. Sulfur concentrations in Scots pine needles were related to the stands' degrees of defoliation. A comparison of the current sulfur concentrations in pine needles from biomonitoring in 2015–2016 with those from previous biomonitoring (in 1983–1985, by Dmuchowski and Bytnerowicz (1995) showed that air quality has improved and SO₂ emissions have decreased.

Harmful algal blooms (HABs) of toxic species of the dinoflagellate genus Dinophysis are a threat to human health as they are mainly responsible for diarrheic shellfish poisoning (DSP) in the consumers of contaminated shellfish. Such contamination leads to shellfish farm closures causing major economic and social issues. The direct effects of numerous HAB species have been demonstrated on adult bivalves, whereas the effects on critical early life stages remain relatively unexplored. The present study aimed to determine the in vitro effects of either cultivated strains of D. sacculus and D. acuminata isolated from France or their associated toxins (i.e. okadaic acid (OA) and pectenotoxin 2 (PTX2)) on the quality of the gametes of the Pacific oyster Crassostrea gigas. This was performed by assessing the ROS production and viability of the gametes using flow cytometry, and fertilization success using microscopic counts. Oocytes were more affected than spermatozoa and their mortality and ROS production increased in the presence of D. sacculus and PTX2, respectively. A decrease in fertilization success was observed at concentrations as low as 0.5 cell mL⁻¹ of Dinophysis spp. and 5 nM of PTX2, whereas no effect of OA could be observed. The effect on fertilization success was higher when both gamete types were concomitantly exposed compared to separate exposures, suggesting a synergistic effect. Our results also suggest that the effects could be due to cell-to-cell contact. These results highlight a potential effect of Dinophysis spp. and PTX2 on reproduction and recruitment of the Pacific oyster.

Microplastic pollution is becoming a major challenge with the growing use of plastic. In recent years, research about microplastic pollution in the environment has become a field of study with increased interest, with ever expanding findings on sources, sinks and pathways of microplastics. Wastewater treatment plants effectively remove microplastics from wastewater and concentrate them in sewage sludge which is often used to fertilise agricultural fields. Despite this, quantification of microplastic pollution in agricultural fields through the application of sewage sludge is largely unknown. In light of this issue, four wastewater treatment plants and 16 agricultural fields (0–8 sewage sludge applications of 20–22 tons ha⁻¹ per application), located in the east of Spain, were sampled. Microplastics were extracted using a floatation and filtration method, making a distinction between light density microplastics (ρ < 1 g cm⁻³) and heavy density microplastics (ρ > 1 g cm⁻³). Sewage sludge, on average, had a light density plastic load of 18,000 ± 15,940 microplastics kg⁻¹ and a heavy density plastic load of 32,070 ± 19,080 microplastics kg⁻¹. Soils without addition of sewage sludge had an average light density plastic load of 930 ± 740 microplastics kg⁻¹ and a heavy density plastic load of 1100 ± 570 microplastics kg⁻¹. Soils with addition of sewage sludge had an average light density plastic load of 2130 ± 950 microplastics kg⁻¹ and a heavy density plastic load of 3060 ± 1680 microplastics kg⁻¹. On average, soils’ plastic loads increased by 280 light density microplastics kg⁻¹ and 430 heavy density microplastics kg⁻¹ with each successive application of sewage sludge, indicating that sewage sludge application results in accumulation of microplastics in agricultural soils.

Evaluating speciation of arsenic (As) is essential to assess its risk in paddy soils. In this study, effects of phosphate on speciation of As in six paddy soils differing in redox status were studied over a range of pH (pH 3-9) and different background calcium (Ca) levels by batch adsorption experiments and speciation modeling. Contrasting effects of phosphate on As speciation were observed in suboxic and anoxic soils. Under suboxic conditions, phosphate inhibited Fe and As reduction probably due to stabilization of Fe-(hydr)oxides, but increased soluble As(V) concentration as a result of competitive adsorption between As(V) and phosphate. In anoxic soils, phosphate stimulated Fe and As reduction and caused increases of As(III) in soil solution under both acidic and neutral/alkaline pH. The LCD (Ligand and Charge Distribution) and NOM-CD (Natural Organic Matter-Charge Distribution) model can describe effects of pH, calcium and phosphate on As speciation in these paddy soils. The results suggest that phosphate fertilization may decrease (at low pH) or increase (at neutral/alkaline pH) As mobility in paddy soils under (sub)oxic conditions, but under anoxic conditions and in phosphorus deficient soils phosphate fertilization may strongly mobilize As by promoting microbial activities.

Among the most used non-steroidal anti-inflammatory drugs (NSAIDs), ketoprofen (KTF) assumes an important position. Nevertheless, its ecotoxicological effects in non-target organisms are poorly characterized, despite its use and frequency of occurrence in aquatic matrices. Thus, the aim of this study was to evaluate the possible toxicological effects of KTF contamination, in two freshwater species, Lemna minor and Daphnia magna, by measuring biochemical, physiological and population parameters. To attain this objective, both species were exposed to KTF at the same concentrations (0, 0.24, 1.2, 6 and 30 μg/L). L. minor plants were exposed during 4 d to these levels of KTF, and the enzymatic activity (catalase (CAT), glutathione S-transferases (GSTs) and carbonic anhydrase (CA)), and pigments content (chlorophylls a, b and total and carotenoids) were analyzed to evaluate the toxicity of this drug. D. magna was acutely and chronically exposed to KTF, and enzymatic activities (CAT, GSTs and cyclooxygenase (COX)), the feeding rates, and reproduction traits were assessed. In L.minor, KTF provoked alterations in all enzyme activities, however, it was not capable of causing any alteration in any pigment levels. On the other hand, KTF also provoked alterations in all enzymatic activities in D. magna, but did not affect feeding rates and life-history parameters. In conclusion, exposure to KTF, provoked biochemical alterations in both species. However, these alterations were not reflected into deleterious effects on physiological and populational traits of L. minor and D. magna.

Despite the now well recognised impact of diclofenac on vultures across the Indian subcontinent, this non-steroidal anti-inflammatory drug (NSAID) was registered in 2013 for livestock treatment in Spain, Europe’s main vulture stronghold. We assessed the risk of exposure to diclofenac and nine other NSAIDs in avian scavengers in the Iberian Peninsula (Spain and Portugal) after the onset of diclofenac commercialization. We sampled 228 livestock carcasses from vulture feeding sites, primarily pig (n = 156) and sheep (n = 45). We also sampled tissues of 389 avian scavenger carcasses (306 Eurasian griffon vultures, 15 cinereous vultures, 11 Egyptian vultures, 12 bearded vultures and 45 other facultative scavengers). Samples were analysed by liquid chromatography with mass spectrometry (LCMS). Seven livestock carcasses (3.07%) contained NSAID residues: flunixin (1.75%), ketoprofen, diclofenac and meloxicam (0.44% each). NSAID residues were only detected in sheep (4.44%) and pig (3.21%) carcasses. Fourteen dead avian scavengers (3.60%) had NSAID residues in kidney and liver, specifically flunixin (1.03%) and meloxicam (2.57%). Flunixin was associated with visceral gout and/or kidney damage in three (0.98%) dead Eurasian griffons. To date, diclofenac poisoning has not been observed in Spain and Portugal, however, flunixin would appear to pose an immediate and clear risk. This work supports the need for well managed carrion disposal, alongside appropriate risk labelling on veterinary NSAIDs and other pharmaceuticals potentially toxic to avian scavengers.