Mercury and rare earth elements (REEs) show different spatial trends in feathers of Kentish plover (Charadrius alexandrinus) breeding along the Adriatic Sea coast, Italy.

Feather analysis is an ethical and effective method for assessing the exposure of wild birds to environmental contamination due to trace elements and organic pollutants. We used feather to monitor the exposure to three toxic and non-essential metals (Hg, Cd, and Pb) and rare earth elements (REEs) of Kentish plover (Charadrius alexandrinus) breeding in different coastal areas (Veneto, Emilia-Romagna, Marche, Abruzzo, and Apulia) along the Italian coast of the Adriatic Sea. Feathers (n = 113) were collected from April to June. Feather concentrations evidenced a significant exposure to Hg (13.05 ± 1.71 mg kg-1 dw) and REEs (447.3 ± 52.8 ng g-1 dw) in the Kentish plover breeding in Veneto (n = 21) compared to the other coastal areas, with several individuals showing Hg concentrations above the adverse effect (5 mg kg-1 dw) and high-risk (9.14 mg kg-1 dw) thresholds reported for birds. Higher REE concentrations compared to Marche (n = 29), Abruzzo (n = 11) and Apulia (n = 13) were also reported for birds breeding in Emilia-Romagna (474.9 ± 41.9 ng g-1 dw; n = 29). The exposure to Cd and Pb was low in all the coastal areas, and only a few samples (n = 6 and n = 4 for Cd and Pb, respectively) exceeded the adverse effect thresholds (0.1 and 4 mg kg-1 for Cd and Pb, respectively). A significant sex-related difference was observed for REE-concentrations, with females showing higher concentration than males. These data highlight the need to monitor the exposure of the Kentish plover to Hg and REEs, especially in the northern basin of the Adriatic Sea, since these elements might negatively affect species' reproductive success and threaten its conservation.

Neonicotinoids and pharmaceuticals in hair of the Red fox (Vulpes vulpes) from the Cavallino-Treporti peninsula, Italy.

Neonicotinoids (NEOs) and active pharmaceuticals ingredients (API) are contaminants widely diffused worldwide, causing increasing concern for potential adverse effects on wildlife. However, research on these contaminants have focused on target and non-target invertebrates, while information on potential effects in terrestrial mammals is lacking. We performed preliminary non-invasive monitoring of NEOs and API in a suburban and agricultural area using hair of the Red fox. The Red fox is a widely diffused mesopredator in Europe, and its plasticity in feeding habits makes it an excellent indicator for assessing exposure to environmental contamination. We observed the presence of NEOs in many Red fox hair samples (n = 11), including imidacloprid (IMI), acetamiprid (ACE), and clothianidin (CLO). The highest quantified concentrations were 6.4 ng g-1 dry weight (dw), 6.7 ng g-1 dw, and 0.9 ng g-1 dw for IMI, ACE, and CLO, respectively. The targeted APIs included non-steroidal anti-inflammatory drugs (NSAIDs) and antidepressants. APIs were less frequently detected than NEOs, and the compounds with the highest prevalence were the NSAID ketoprofen (36%), the antidepressant sertraline (36%), and its active metabolite norsertraline (27%). The presence of human pharmaceuticals such as the NSAID ibuprofen and the antidepressants sertraline, fluoxetine, and their active metabolites norsertraline and norfluoxetine suggest environmental contamination due to untreated and partially treated wastewater discharged in surface waters and soils of the study area. The detection and quantification of ketoprofen and flunixin also suggest the possible use of contaminated manure on farmland. Findings indicate that hair may be used for monitoring environmental exposure to NEOs and provide evidence that hair is a good marker of exposure for antidepressants and certain NSAIDs, including ibuprofen, ketoprofen, and flunixin.

The ubiquity of neonicotinoid contamination: Residues in seabirds with different trophic habits.

Neonicotinoids are one of the most diffusely used classes of pesticides whose level of danger toward non-target invertebrate and vertebrate species has raised increasing concern in the last decades. Among vertebrates, birds are particularly susceptible to unintentional neonicotinoid poisoning since they can be exposed through different pathways, including ingestion of dressed seeds, sucking of contaminated pollen, ingestion of sprayed insects, predation on contaminated aquatic and terrestrial preys. In the present study, we investigated the possible exposure of seabirds by measuring the residues of five neonicotinoids (acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam) in samples of pooled feathers collected from fledglings of the strictly piscivorous Sandwich tern (Thalasseus sandvicensis) and the mixotrophic species Mediterranean gull (Ichthyaetus melanocephalus). At least one neonicotinoid was quantified in all the Mediterranean gull samples (n = 11) and 89% of the analysed Sandwich tern samples (n = 36). The active principles with the highest quantification rates were imidacloprid (100% in Mediterranean gulls and 58% in Sandwich terns) and clothianidin (100% in Mediterranean gulls and 61% in Sandwich terns), while thiacloprid was the less frequently detected pesticide (<20% of samples in both species). Mean concentrations ± standard error for imidacloprid, clothianidin and thiamethoxam were 8.8 ± 1.4, 4.5 ± 0.19 and 0.16 ± 0.02 ng g-1 for the Mediterranean gull, and 5.8 ± 0.55, 0.60 ± 0.08 and 0.36 ± 0.03 ng g-1for the Sandwich tern, respectively. Our data evidenced the exposure of seabirds to neonicotinoids and the further need to investigate the extent of neonicotinoid contamination in non-agricultural ecosystems.

Occurrence of rare earth elements in fledgelings of Thalasseus sandvicensis.

Rare Earth Elements (REEs) are increasingly exploited for crucial new technologies, and their massive use in the past decades has significantly increased their environmental concentrations. Although their effects have been extensively studied in vitro and in vivo in model species, little is known of their accumulation and potential toxic effects in wildlife, including waterbirds. In the present work, we measured the concentrations of REEs in feathers of young Sandwich tern (Thalasseus sandvicensis) about 16-20 days old to assess whether the accumulation of these elements may be a concern in Venice's Lagoon, one of the most important wetlands of the Mediterranean area for breeding and migrating birds. The REE concentrations detected in the Sandwich tern were the highest among those reported in the literature for bird's feathers (940.9 ± 223.0 ng g-1), although in the study area industrial activities related to REEs mining, processing and disposal are absent. In particular, Lanthanum (La) was more abundant in the feathers than other REEs and accounted for 73-97% of total REEs detected. Analysis of bird's food indicated that diet is a relevant route of exposure to REEs for young terns; however, concentration in fishes are relevantly higher than in the feathers for all REEs other than La. The study evidenced the need to collect more information concerning the occurrence of REEs both in the abiotic matrices (i.e. water and sediments) and in living organisms of different trophic levels to improve the general knowledge concerning the fate of REEs in the aquatic ecosystems.

Seabirds as Biomonitors of Mercury Bioavailability in the Venice Lagoon.

Seabirds accumulate mercury (Hg) due to their long-life span together with their high trophic position. A Hg monitoring in Venice's Lagoon using three seabird species occupying different trophic habitat (Thalasseus sandvicensis, Ichthyaetus melanocephalus, and Chroicocephalus ridibundus) confirmed that fledgelings might effectively be used as sentinels of Hg bioavailability. The significant differences in Hg residues in feathers observed among the species highlighted a possible differential exposure due to different diets, with C. ridibundus accumulating more Hg than the other species. Average residues in feathers were not above the threshold associated with adverse effects on birds (5 mg kg- 1). Nevertheless, a large part of the C. ridibundus individuals (58%) exceeded the adverse effect level, underlining the need for strengthening Hg monitoring. Seabirds indeed may provide relevant insight on Hg transfer in food webs and a better picture of the hazards to men when bird species forage on species exploited for human consumption.

Fragrance materials (FMs) affect the larval development of the copepod Acartia tonsa: An emerging issue for marine ecosystems.

Fragrance materials (FMs) are used in a variety of detergents and cosmetics, including household and personal care products. Despite their widespread use and the growing evidence of their occurrence in surface waters worldwide, very little is known about their toxicity towards marine species, including a key component of the marine food webs such as copepods. Thus, we investigated the toxicity of six of the more long-lasting and stable commercial fragrances, including Amyl Salicylate (AMY), Oranger Crystals (ORA), Hexyl Salicylate (HEX), Ambrofix (AMB), Peonile (PEO), and Benzyl Salicylate (BZS), to assess their ability to impair the larval development of the calanoid copepod Acartia tonsa. FMs inhibited the development of A. tonsa significantly at concentrations by far lower than the effect-concentrations reported in the literature for aquatic species. The more toxic FMs were HEX (EC50 = 57 ng L-1), AMY (EC50 = 131 ng L-1) and ORA (EC50 = 766 ng L-1), while the other three compounds exerted toxic effects at concentrations higher than 1000 ng L-1 (LOEC at 1000 ng L-1 for PEO and BZS, and at 10,000 ng L-1 for AMB). Early life-stage mortality was unaffected by FMs at all the tested concentrations. A comparison with water concentrations of FMs reported in the literature confirmed that FMs, especially HEX and AMY, may act as contaminants of potential concern in many aquatic habitats, including urban areas and remote and polar environments.

An Integrated Testing Strategy (ITS) to assess the environmental compatibility of wood protection techniques.

To quantify the possible impact of different wood protection techniques on the aquatic environment, we applied a tiered Integrated Testing Strategy (ITS) on leachates obtained from untreated (UTW) Norway spruce (Picea abies), specimens treated with a copper-ethanolamine-based preservative solution, complying with the Use Class 3 (UC3), and specimens thermally modified (TM). Different maturation times in water were tested to verify whether toxicant leaching is time-dependent. Tier I tests, addressing acute effects on Aliivibrio fischeri, Raphidocelis subcapitata, and Daphnia magna, evidenced that TM toxicity was comparable or even lower than in UTW. Conversely, UC3 significantly affected all species compared to UTW, also after 30 days of maturation in water, and was not considered an environmentally acceptable wood preservation solution. Tier II (effects on early-life stages of Lymnea auricularia) and III (chronic effects on D. magna and L. auricularia) performed on UTW and TM confirmed the latter as an environmentally acceptable treatment, with increasing maturation times resulting in decreased adverse effects. The ITS allowed for rapid and reliable identification of potentially harmful effects due to preservation treatments, addressed the choice for a less impacting solution, and can be effective for manufacturers in identifying more environmentally friendly solutions while developing their products.

Impacts of exhaust gas cleaning systems (EGCS) discharge waters on planktonic biological indicators.

Exhaust Gas Cleaning Systems (EGCS), operating in open-loop mode, continuously release acidic effluents (scrubber waters) to marine waters. Furthermore, scrubber waters contain high concentrations of metals, polycyclic aromatic hydrocarbons (PAHs), and alkylated PAHs, potentially affecting the plankton in the receiving waters. Toxicity tests evidenced significant impairments in planktonic indicators after acute, early-life stage, and long-term exposures to scrubber water produced by a vessel operating with high sulphur fuel. Acute effects on bacterial bioluminescence (Aliivibrio fischeri), algal growth (Phaeodactylum tricornutum, Dunaliella tertiolecta), and copepod survival (Acartia tonsa) were evident at 10 % and 20 % scrubber water, while larval development in mussels (Mytilus galloprovincialis) showed a 50 % reduction at ∼5 % scrubber water. Conversely, larval development and reproductive success of A. tonsa were severely affected at scrubber water concentrations ≤1.1 %, indicating the risk of severe impacts on copepod populations which in turn may result in impairment of the whole food web.

Spiking organic chemicals onto sediments for ecotoxicological analyses: an overview of methods and procedures.

Laboratory testing with spiked sediments with organic contaminants is a valuable tool for ecotoxicologists to study specific processes such as effects of known concentrations of toxicants, interactions of the toxicants with sediment and biota, and uptake kinetics. Since spiking of the sediment may be performed by using different strategies, a plethora of procedures was proposed in the literature for spiking organic chemicals onto sediments to perform ecotoxicological analyses. In this paper, we reviewed the scientific literature intending to characterise the kind of substrates that were used for spiking (i.e. artificial or field-collected sediment), how the substrates were handled before spiking and amended with the organic chemical, how the spiked sediment was mixed to allow the homogenisation of the chemical on the substrate and finally how long the spiked sediment was allowed to equilibrate before testing. What emerged from this review is that the choice of the test species, the testing procedures and the physicochemical properties of the organic contaminant are the primary driving factors affecting the selection of substrate type, sediment handling procedures, solvent carrier and mixing method. Finally, we provide recommendations concerning storage and characterization of the substrate, equilibrium times and verification of both equilibration and homogeneity.

Assessing the exposure to human and veterinary pharmaceuticals in waterbirds: The use of feathers for monitoring antidepressants and nonsteroidal anti-inflammatory drugs.

Exposure to active pharmaceutical ingredients (APIs) from both human and veterinary sources is an increasing threat to wildlife welfare and conservation. Notwithstanding, tracking the exposure to pharmaceuticals in non-target and sensitive vertebrates, including birds, is seldom performed and relies almost exclusively on analysing internal organs retrieved from carcasses or from experimentally exposed and sacrificed birds. Clearly, this excludes the possibility of performing large-scale monitoring. Analysing feathers collected from healthy birds may permit this, by detecting APIs in wild birds, including protected and declining species of waterbirds, without affecting their welfare. To this end, we set up a non-destructive method for analysing the presence of non-steroidal anti-inflammatory drugs (NSAIDs), selective serotonin reuptake inhibitors (SSRIs) and noradrenaline reuptake inhibitors (SNRIs) in the feathers of fledglings of both the Mediterranean gull (Ichtyaetus melanocephalus) and the Sandwich tern (Thalasseus sandvicensis). The presence of several NSAIDs and SSRIs above the method quantification limits have confirmed that feathers might be a suitable means of evaluating the exposure of birds to APIs. Moreover, the concentrations indicated that waterbirds are exposed to NSAIDs, such as diclofenac, ibuprofen and naproxen, and SSRIs, such as citalopram, desmethylcitalopram, fluvoxamine and sertraline, possibly due to their widespread use and incomplete removal in wastewater treatment plants (WWTPs). The active ingredient diclofenac raises a the primary concern for the ecosystem and the welfare of the waterbirds, due to its high prevalence (100% and 83.3% in Mediterranean gull and Sandwich tern, respectively), its concentrations detected in feathers (11.9 ng g-1 and 6.7 ng g-1 in Mediterranean gull and Sandwich tern, respectively), and its documented toxicity toward certain birds.

Inhibition of Larval Development of Marine Copepods Acartia tonsa by Neonicotinoids.

Neonicotinoids (NEOs) are neurotoxic pesticides widely used in agriculture due to their high effectiveness against pest insects. Despite their widespread use, very little is known about their toxicity towards marine organisms, including sensitive and ecologically relevant taxa such as copepods. Thus, we investigated the toxicity of five widely used NEOs, including acetamiprid (ACE), clothianidin (CLO), imidacloprid (IMI), thiacloprid (THI), and thiamethoxam (TMX), to assess their ability to inhibit the larval development of the copepod Acartia tonsa. The more toxic NEOs were ACE (EC50 = 0.73 µg L-1), TMX (EC50 = 1.71 µg L-1) and CLO (EC50 = 1.90 µg L-1), while the less toxic compound was IMI (EC50 = 8.84 µg L-1). Early life-stage mortality was unaffected by NEOs at all of the tested concentrations. The calculated toxicity data indicated that significant effects due to ACE (EC20 = 0.12 µg L-1), THI (EC20 = 0.88 µg L-1) and TMX (EC20 = 0.18 µg L-1) are observed at concentrations lower than established chronic aquatic life benchmarks reported by USEPA for freshwater invertebrates. Nevertheless, since environmental concentrations of NEOs are generally lower than the threshold concentrations we calculated for A. tonsa, the effects may be currently of concern only in estuaries receiving wastewater discharges or experiencing intense runoff from agriculture.

Long-term effects of neonicotinoids on reproduction and offspring development in the copepod Acartia tonsa.

Neonicotinoids (NEOs) are neurotoxic pesticides acting as nicotinic acetylcholine receptor agonists. NEOs' efficacy against pest insects has favoured their spreading use in agriculture, but their proven effectiveness against non-target insects in terrestrial and aquatic ecosystems also raised concern over their environmental impact. Crustaceans were often studied for the impacts of NEOs due to their economic values and nervous' system similarity with insects. However, most studies on crustaceans focused on acute effects or exposure of early-life stages, while long-term effects were seldom explored. The present study aimed to assess the potential long-term effects of four commercially available NEOs on the reproduction and offspring of the calanoid copepod Acartia tonsa, a key species in the food webs of several coastal and estuarine environments. NEOs were confirmed as potent interferents of copepod reproduction. The first-generation compound acetamiprid significantly inhibited egg production and hatching ratio at 10 ng L-1, while larval survival and development were affected at 81 ng L-1. Similarly, the first-generation compound thiacloprid significantly inhibited the hatching ratio and larval development at 9 ng L-1, while it did not affect egg production and larval survival. Second-generation compounds were less toxic than acetamiprid and thiacloprid: clothianidin affected significantly only larval development of the offspring at 62 ng L-1, while thiamethoxam was not toxic at both the tested concentrations (8 ng L-1 and 84 ng L-1). These data evidenced that effects on copepods may occur at concentrations below the chronic aquatic life benchmarks reported by USEPA for acetamiprid (2100 ng L-1) and thiacloprid (970 ng L-1), suggesting that long-term effects of NEOs have been underestimated. A comparison with environmental concentrations evidenced that NEO-mediated effects on copepods are more liable in coastal areas receiving discharge from wastewater treatment plants or diffuse inputs from agricultural land during pesticide application periods.