Water quality effects of peat rewetting and leftover conifer brash, following peatland restoration and tree harvesting.

Harvesting of plantation conifers on peatlands is carried out as part of restoration and forestry operations. In particular, in the UK and Ireland, conifer plantations on drained ombrotrophic blanket and raised bogs are increasingly being removed (by harvesting), along with blocking of drainage ditches to help raise water tables to reinitiate and restore bog vegetation and function. However, both tree harvesting and peatland restoration operations can have significant impacts on water quality at local and catchment scales. Previous research has suggested that leaching from leftover decomposing brash (tree tops and branches, including wood and needles) is the primary cause, while other work has suggested that release from rewetted peat also contributes to water quality changes. This research investigates the relative importance of peat rewetting, needles and branches on water quality using mesocosm experiments, to help elucidate the mechanisms behind water quality changes following restoration and harvesting operations. Peat and brash were collected from a drained afforested blanket bog in the Flow Country, Scotland. Short-term mesocosm experiments were conducted by incubating peat, peat + needles and peat + needles + branches with rainwater in quadruplicate. Brash from Sitka spruce (Picea sitchensis) and lodgepole pine (Pinus contorta) was investigated separately, while we also conducted experiments with fresh and aged (∼18 months) brash. Peat, needles and branches all significantly impacted water quality in the order of branches > needles > peat, while concentrations of DOC, PO43-, NH4+, K and Mn were most impacted. Water quality impacts of spruce brash appeared generally greater than pine, while fresh brash had larger effects than aged brash. In our mesocosms, relative contributions to water quality changes were estimated by elemental yields. On average, peat contributed 25.4% (range 0.6-72.3%), while needles and brash contributed 19.7% (range 3.0-37.0%) and 54.9% (range 22.1-70.2%) to yields, respectively. We further estimate that 267 kg C ha-1 (255.8 kg as DOC, 10.7 kg as DIC), 27.4 kg K ha-1, 5.8 kg P ha-1 (as PO43-) and 0.5 kg N ha-1 (as NH4+) could be released from brash, over nine days.

Comparison of two carbonaceous supported Fe-rich adsorbents for arsenate removal: A functionalisation and mechanistic study with applicability to groundwater treatment.

The presence of arsenic in groundwater, and through this in drinking water, has been shown to present a serious risk to public health in many regions of the world. In this study, two iron-rich carbonous adsorbents were compared for the removal of arsenate (As(V)) from groundwater. Biochars (FeO-biochar and FeO-pyrochar) derived from biomass waste were functionalised in two different ways with iron chloride for comparation. Batch and dynamic parameters were optimised to achieve >99% As(V) removal efficiency. Experimental data were best described by the pseudo-second order kinetic model, while multi-stage diffusion appeared to limit mass transfer of As(V). Among the isotherm models evaluated, the Freundlich model best described the experimental results with high correlation coefficients (R2 ≥ 0.94) for both adsorbents. Monolayer adsorption capacities were found to be 4.34 mg/g and 8.66 mg/g for FeO-biochar and FeO-pyrochar, respectively. Batch studies followed by instrumental characterisation of the materials indicated the removal mechanisms involved to be electrostatic interactions (outer-sphere), OH- ligand exchange (inner-sphere complexation) and hydrogen bonding with functional groups. Higher pHpzc (9.1), SBET (167.2 m2/g), and iron/elemental content for the FeO-pyrochar (compared with the FeO-biochar) suggested that both surface chemistry and porosity/surface area were important in adsorption. Dynamic studies showed FeO-pyrochar can be used to remove As(V) from groundwater even at low 'environmental' concentrations relevant to legislative limits (<10 µg/L), whereby 7 g of FeO-pyrochar was able to treat 5.4 L groundwater.

Comparing DNA isolation and sequencing strategies for 16S rRNA gene amplicon analysis in biofilm containing environments.

Bacteria are primarily responsible for biological water treatment processes in constructed wetland systems. Gravel in constructed wetlands serves as an essential substrate onto which complex bacterial biofilms may successfully grow and evolve. To fully understand the bacterial community in these systems it is crucial to properly isolate biofilms and process DNA from such substrates. This study looked at how best to isolate bacterial biofilms from gravel substrates in terms of bacterial richness. It considered factors including the duration of agitation during extraction, extraction temperature, and enzyme usage. Further, the 16S taxonomy data subsequently produced from Illumina MiSeq reads (using the SILVA 132 ribosomal RNA (rRNA) database on the DADA2 pipeline) were compared with the 16S data produced from Oxford Nanopore Technologies (ONT) MinION reads (using the NCBI 16S database on the EPI2ME pipeline). Finally, performance was tested by comparing the taxonomy data generated from the Illumina MiSeq and ONT MinION reads using the same (SILVA 132) database. We found no significant differences in the effective number of species observed when using different bacterial biofilm detachment techniques. However, enzyme treatment enhanced the total concentration of DNA. In terms of wetland community profiles, relative abundance differences within each sample type were clearer at the genus level. For genus-level taxonomic classification, MinION sequencing with the EPI2ME pipeline (NCBI database) produced bacterial abundance information that was poorly correlated with that from the Illumina MiSeq and DADA2 pipelines (SILVA132 database). When using the same database for each sequencing technology (SILVA132), the correlation between relative abundances at genus-level improved from negligible to moderate. This study provides detailed information of value to researchers working on constructed wetlands regarding efficient biofilm detachment techniques for DNA isolation and 16 s metabarcoding platforms for sequencing and data analysis.

Difference in concentration of lead (Pb) in meat from pheasants killed using lead and iron (Fe) shotgun ammunition.

The use of lead shotgun ammunition for hunting has been banned in a few jurisdictions and habitats, principally to protect wild birds from poisoning by ingestion of spent lead shot. The EU and UK REACH processes have recently considered bans on lead ammunition throughout the European Union and United Kingdom, including assessments of possible health benefits from reduced human dietary exposure to lead from game meat. Comparisons of the mean lead concentrations in meat from gamebirds killed using lead and non­lead shotgun ammunition have not been published. We compared lead concentrations in meat from wild-shot pheasants from which lead shotgun pellets were recovered (n = 27) with those from which iron pellets were recovered (n = 20), having removed all pellets from the meat before analysis. The mean concentration of lead in meat from pheasants killed using lead shot was 2.10 mg/kg w.w., which is >20 times the European Union's maximum permitted level for the lead concentration in meat from domesticated animals. For pheasants killed using iron shot the mean was 0.07 mg/kg w.w., which is below the maximum permitted level.

Medicated livestock carcasses and landfill sites: Sources of highly toxic veterinary pharmaceuticals and caffeine for avian scavengers.

Veterinary drugs are of concern in terms of potential environmental pollution and their negative impacts on avian scavengers. These pharmaceuticals reach vultures through the consumption of carcasses of previously treated livestock. Here, we analysed samples from livestock carcasses (n = 159), avian scavenger tissues (n = 116) and plasma (n = 312) for 49 compounds commonly used in veterinary medicine in Aragon (NE Spain) and nearby regions. Samples were analysed using liquid chromatography with electrospray ionization mass spectrometry (LC-ESI-MS/MS). We detected pharmaceuticals in 54.1% of livestock carcasses analysed (50.3% with antibiotics, 10.8% with NSAIDs). For veterinary pharmaceuticals in tissues and plasma from avian scavengers, we detected pharmaceuticals in 51.7% and 28.5% of samples, respectively. Antibiotics were detected in 50.9% and 25.3% while NSAIDs were determined in 6.0% and 5.5% of tissues and plasma from avian scavengers, respectively. Moreover, caffeine was detected in plasma in 73.7% of vultures sampled at landfill sites, indicating its usefulness as a biomarker of urban garbage ingestion. We found an association between livestock carcasses, especially pigs and chickens, and the presence of veterinary pharmaceuticals in avian scavengers. We highlight that carcass disposal for feeding avian scavengers must address the potential risks posed by veterinary pharmaceutical residues.

Removal of benzotriazole derivatives by biochar: Potential environmental applications.

Benzotriazole and its derivatives (BTAs) are commonly present in wastewater due to their extensive use in industrial processes, yet their removal is still unexplored. Here, we test the removal of these pollutants using two functionalised biochars, synthesised from wild plum (WpOH) and apricot (AsPhA) kernels. The aim of this work was to optimise the adsorption process against various BTAs (i.e., benzotriazole (BTZ), 4-hydroxy-1H-benzotriazole (OHBZ), 4-methyl-1H-benzotriazole (4 MBZ), 5-methyl-1H-benzotriazole (5 MBZ), 5-chloro-1H-benzotriazole (ClBZ), 5,6-dimethyl-1H-benzotriazole (DMBZ)), and determine the adsorption mechanisms at play, using real wastewater matrices. Batch studies showed that the optimal adsorption pH ranged between 4 and 6 for WpOH and AsPhA, respectively, and equilibrium was reached after 240 min. The kinetic models that best described the adsorption process were in the following order: Elovich model > pseudo-second order model > pseudo-first order model. The equilibrium data showed the highest correlation with the Freundlich isotherm, indicating multilayer adsorption. The maximum adsorption capacity obtained in mixtures was 379 mg/g on WpOH and 526 mg/g on AsPhA. The mechanistic work revealed that the BTAs became bound to the biochar primarily through H-bonding, n-π and π-π EDA interactions. In wastewater, obtained before and after conventional treatment, the concentration of OHBZ and BTZ was reduced by >40%, while the concentration of the other compounds studied fell below the detection limit (∼2.0-90 ng/L). Finally, using a Vibrio fischeri assay, we showed that adsorption onto AsPhA significantly reduced the relative toxicity of both raw and treated wastewater.

Lead concentrations in commercial dogfood containing pheasant in the UK.

UK and EU regulators are evaluating the potential health benefits of restricting the use of lead ammunition. Little information is available on exposure of pets to ammunition-derived dietary lead from petfood containing meat from wild-shot game animals. We found dogfood including wild-shot pheasant meat to be widely available in the UK. 77% of samples from three raw pheasant dogfood products exceeded the EU maximum residue level (MRL) for lead in animal feed, with mean concentrations approximately 245, 135 and 49 times above the MRL. Concentrations > MRL were also found in a dried food containing pheasant, but not in a processed food, nor in chicken-based products. Lead concentrations in raw pheasant dogfood considerably exceeded those in pheasant meat sold for human consumption, possibly because the dogfood mincing process further fragmented lead particles from shot. Dogs frequently consuming such high-lead food risk adverse health effects; this should be considered within decision-making processes about regulation.

Pilot-scale phosphate recovery from wastewater to create a fertiliser product: An integrated assessment of adsorbent performance and quality.

Eutrophication and the predicted limited future availability of rock phosphate has triggered the increased development of phosphorus (P) recovery technologies, however, for remote regions, recovery solutions are still limited. Here, we report on a novel pilot-scale technology (FILTRAFLOTM-P reactor) to recover phosphate (PO43-) from wastewater effluent through a filtration/adsorption process in a rural setting. This unit employs enhanced gravitational filtration through adsorption media (here, a novel KOH deacetylated crab carapace based chitosan-calcite material (CCM)) with continuous self-backwashing. Trials were designed to assess how the FILTRAFLOTM-P unit would operate under 'real' conditions (both at low and high PO43- levels), and to ascertain the effectiveness of the adsorbent to recover phosphate from final effluent. High removal was achieved at low phosphate concentrations, bringing the residual effluent PO43- level below 1 mg/L (EU limit for sensitive water bodies), while phosphate was efficiently harvested (at more than 50%) at higher PO43- levels. Surface microprecipitation and inner-sphere complexation were postulated as the main PO43- adsorption mechanisms through XRD, XPS and EDX elemental mapping. Further, a quality assessment of the P-enriched CCM (which could be used as a potential soil amendment) was undertaken to consider elemental composition, microbiological assessment and quantification of organic micropollutants. Quality analysis indicated ∼2.5% P2O5 present, trace levels (well below legislative limits) of heavy metals and extremely low levels of organic pollutants (e.g., PCBs, pharmaceuticals). No detectable levels of target bacterial pathogens were observed. Pot trials showed that ryegrass cultivated with the addition of the CCM adsorbent achieved higher plant dry matter and P concentration when compared to unfertilised controls, with a slow-release kinetic pattern. This study showed that CCM used with the FILTRAFLOTM-P pilot reactor has high potential to recover phosphate from effluents and encourage resource recovery via bio-based management of waste.

Antimicrobial resistant Escherichia coli in Scottish wild deer: Prevalence and risk factors.

Antimicrobial resistance (AMR) is a recognised threat to global health. Obtaining data on the prevalence of AMR in environmental bacteria is key to understanding drivers and routes of transmission. Here, 325 Shiga toxin negative deer faecal samples-gathered from across the Scottish mainland-were screened for the presence of AMR Escherichia coli and investigated for potential risk factors associated with AMR occurrence. E. coli with resistance to antimicrobials of clinical health concern, including carbapenems and 3rd generation cephalosporins, were targeted. Ninety-nine percent of samples yielded E. coli, and the prevalence of resistant E. coli at the level of faecal samples was 21.8% (n = 71) for tetracycline, 6.5% (n = 21) for cefpodoxime, 0.3% for ciprofloxacin (n = 1), with no recorded resistance to meropenem. Potential risk factors for tetracycline and cefpodoxime resistance were investigated. The presence of broadleaved woodlands was significantly associated with both AMR phenotypes, which may relate to land use within or around such woodlands. Associated risk factors varied across resistance phenotype and deer species, with proximity or density of horses an indicator of significantly decreased and increased risk, respectively, or tetracycline and cefpodoxime resistance in E. coli from roe deer, but not from red deer. Distance from wastewater treatment plants was a significant risk factor for tetracycline resistance in E. coli from red deer but not from roe deer. Data indicated that AMR E. coli can occur in wild deer populations that are not directly exposed to the selective pressure exerted by antimicrobial treatment. Overall, resistance to critically important antimicrobials was found to be low in the studied population, suggesting no immediate cause for concern regarding human health. Utilising existing culling frameworks, wild deer in Scotland could function well as a sentinel species for the surveillance of AMR in the Scottish environment.

Implications for food safety of the size and location of fragments of lead shotgun pellets embedded in hunted carcasses of small game animals intended for human consumption.

Carcasses of common pheasants (Phasianus colchicus) killed by hunters using shotguns are widely used or sold in the United Kingdom and elsewhere for human consumption. Almost all of the birds are shot using shotgun pellets composed principally of lead (Pb). Lead shotgun pellets often fragment on impact within the bodies of gamebirds, leaving small lead particles in the meat that are difficult for consumers to detect and remove and from which a greater proportion of lead is likely to be absorbed. Chronic exposure to even low levels of lead is associated with negative health effects in humans and especially in groups particularly vulnerable to the effects of lead, which include young children and pregnant women. Our study used a high-resolution computerised tomography X-ray scanner to locate, in three dimensions, metal fragments embedded within carcasses of eight pheasants sold for human consumption in the UK. Small radio-dense fragments (<2 mm diameter), assumed to be metallic lead, were present in all of the pheasant carcasses examined (mean number: 39 per carcass) and many were too small (<0.1 mm diameter) and too distant from the nearest large shotgun pellet for it to be practical for consumers to detect and remove them without discarding a large proportion of otherwise usable meat. Consumers of carcasses of pheasants killed using lead shotgun ammunition are likely to be exposed to elevated levels of dietary lead, even if careful food preparation is practiced to remove shotgun pellets and the most damaged tissue.

Determinants of the exposure of Eurasian griffon vultures (Gyps fulvus) to fluoroquinolones used in livestock: The role of supplementary feeding stations.

Veterinary pharmaceuticals, including antibiotics, are emerging contaminants of concern worldwide. Avian scavengers are exposed to pharmaceuticals through consumption of livestock carcasses used for feeding wildlife for conservation purposes at supplementary feeding stations. Here we tested the hypothesis that griffon vultures (Gyps fulvus) would be more exposed to antibiotics (i.e., quinolones) when feeding on livestock carcasses from intensive farming than when they rely on carcasses from extensive farming or wild animals. We sampled 657 adult griffon vultures captured between 2008 and 2012. In addition, we sampled tissues from domestic livestock supplied at feeding stations in the study area between 2009 and 2019; pig (n = 114), sheep (n = 28), cow (n = 1) and goat (n = 2). Samples were analysed by liquid chromatography with electrospray ionization mass spectrometry (LC-ESI-MS). Quinolones were detected in plasma from 12.9% of the griffon vultures analysed. Quinolone prevalence in griffon vultures varied significantly among feeding stations but was also affected by the total amount of carcasses supplemented, especially the mass of pig carcasses. These results aligned with a 21.1% quinolone prevalence in pig carcasses sampled at feeding stations, wherein enrofloxacin and ciprofloxacin levels of up to 3359 ng/g and 1550 ng/g, respectively, were found. Given enrofloxacin pharmacokinetics in pig tissues, 5.3% of the analysed pigs may have died no more than one day after treatment. Quinolone presence in vultures was negatively associated with blood lead levels, which mostly originates from lead ammunition and indicates a higher consumption of game animal carcasses. Carcass disposal for feeding avian scavengers must always assess and manage the risks posed by veterinary pharmaceuticals, especially when livestock provided may have died soon after treatment.

How contaminated with ammunition-derived lead is meat from European small game animals? Assessing and reducing risks to human health.

Small game animals are generally hunted with lead gunshot which often fragments causing elevated lead concentrations in meat and presenting health risks to frequent consumers and vulnerable groups. We reviewed three decades of European data on lead concentrations in the meat of gamebirds, rabbits and hares across countries with various restrictions on lead gunshot use. Mean meat lead concentrations decreased to a low level in Denmark, the only country in the study with a total ban on lead gunshot use. In contrast, elsewhere in Europe meat lead concentrations increased over time, an unexplained and previously undescribed finding. The only regulatory restriction associated with a decrease in meat lead concentrations was the Danish total ban on lead gunshot use. We calculated an arithmetic mean lead concentration in small game meat of 5.205 ppm w.w. (2011-2021) from across Europe. EU and UK regulators are considering banning lead ammunition for all hunting to protect human and wildlife health. The mean value we found for small game meat (2011-2021) was fourteen times higher than that used in a recent EU-wide risk assessment.

Mercury speciation in Scottish raptors reveals high proportions of inorganic mercury in Scottish golden eagles (Aquila chrysaetos): Potential occurrence of mercury selenide nanoparticles.

Knowledge of the uptake and fate of mercury (Hg) compounds in biota is important in understanding the global cycling of Hg and its transfer pathways through food chains. In this study, we analysed total mercury (T-Hg) and methylmercury (MeHg) concentrations in 117 livers of Scottish birds of prey that were found across Scotland and submitted for post-mortem examination through the Raptor Health Scotland project between 2009 and 2019. Statistical comparisons focussed on six species (barn owl, Tyto alba; Eurasian common buzzard, Buteo buteo; golden eagle, Aquila chrysaetos; hen harrier, Circus cyaneus; Eurasian sparrowhawk, Accipiter nisus; and tawny owl, Strix aluco) and showed that golden eagles had a statistically lower fraction of MeHg compared to other raptor species. Further investigation using stable carbon and stable nitrogen isotope ratio measurements carried out for the golden eagles (n = 15) indicated that the increased presence of inorganic mercury (iHg) correlated with a marine influence on the primarily terrestrial diet. Additional bioimaging (n = 1) with laser ablation - inductively coupled plasma - mass spectrometry indicated the co-location of Hg and selenium (Se) within the liver tissue and transmission electron microscopy showed evidence of nanoparticles within the range of 10-20 nm. Further analysis using single particle - inductively coupled plasma - mass spectrometry (n = 4) confirmed the presence of Hg nanoparticles. Together, the evidence suggests the presence of mercury selenide (HgSe) nanoparticles in the liver of some golden eagles that, to our knowledge, has never been directly observed in terrestrial birds of prey. This study points to two alternative hypotheses: these golden eagles may be efficient at breaking down MeHg and form HgSe nanoparticles as a detoxification mechanism (as previously observed in cetaceans), or some golden eagles with elevated iHg may have accumulated these nanoparticles by foraging on stranded cetaceans or seabirds.

Effect of long-term storage and harvest site on the fatty acid profiles, mineral and antioxidant properties of selected edible Scottish seaweeds.

The limited understanding of the effect of pre-and post-harvest techniques still hinders the full exploitation of seaweed. Here, the effect of harvest site, long term storage and species on the elemental composition, fatty acid profile, lipid content, and antioxidant properties were determined in eight intertidal seaweed species common to Scotland, harvested for potential food application and stored for up to 128 weeks. Result showed that the most significant variation was due to species, with no statistical link found for the combined interaction effect of both storage duration and harvest site in most cases, except for the antioxidant parameters and some selected elements, which was limited to some seaweed species. Overall, our result showed that the chemical profiles of the seaweed species studied were remarkably consistent and unaffected by long term storage. Thus, suggesting that seaweeds sampled from Scotland could be a valuable resource for the development of functional foods.

Enhanced phosphate removal and potential recovery from wastewater by thermo-chemically calcinated shell adsorbents.

Shell from the seafood processing industry is an under-utilised waste resource worldwide. Calcite, the major component of shell is commonly used in wastewater treatment for the removal of phosphorus (P). Here, mussel and oyster shell-based adsorbents (MSB and OSB) were used for removal of P as phosphate (PO43-) from aqueous solution and secondary wastewater, following preparation through chemical calcination at 700 °C. Batch adsorption experiments were carried out to identify the effects of various operating parameters (e.g., pH, dosage, contact time, initial concentration of P ions, co-existing ions), while a desorption study helped to understand the availability of the bonded P. The optimal contact time for PO43- removal was 120 min using both adsorbents with the dose at 200 mg. Characterisation of the adsorbent was performed using SEM-EDX, pHpzc, BET, FTIR and XRD. The XRD analysis showed that both calcite and lime were present on the surface of the shell particles. P was adsorbed effectively through inner-sphere complexation and surface microprecipitation mechanisms, while an enhanced maximum P adsorption capacity of 12.44 mg/g for MSB and 8.25 mg/g for OSB was reached. The Redlich-Peterson isotherm model fitted well with the equilibrium isotherm data (R2 ≥ 0.97) which also suggested a heterogenic surface. The desorption study (on the saturated adsorbent) found that ~97% of bonded P could be plant available in soil. These results suggest that a shell-based adsorbent can serve as a promising material for P removal from real wastewater effluent and subsequently could be used as a soil conditioner.

The non-steroidal anti-inflammatory drug nimesulide kills Gyps vultures at concentrations found in the muscle of treated cattle.

Throughout South Asia, cattle are regularly treated with non-steroidal anti-inflammatory drugs (NSAIDs) and their carcasses are left for scavengers to consume. Residues of the NSAID diclofenac in cattle carcasses caused widespread mortality and catastrophic population declines in three species of Gyps vulture during the 1990s and 2000s. Diclofenac is now banned, but other NSAIDs are used in its place. Different lines of evidence, including safety testing in Gyps vultures, have shown that some of these other NSAIDs are toxic, or probably toxic, to vultures. The NSAID nimesulide is widely available and commonly used, and has been found in dead vultures with signs of renal failure (i.e. visceral gout) and without the presence of diclofenac and/or other vulture-toxic NSAIDs. Nimesulide is therefore probably toxic to vultures. Here, we report safety testing of nimesulide in Gyps vultures. In a controlled toxicity experiment, we gave two vultures the maximum likely exposure (MLE) of nimesulide calculated from initial pharmacokinetic and residue experiments in cattle. Two other control birds were given an oral dose of water. Both vultures dosed with nimesulide died within 30 h, after showing outward signs of toxicity and increases in biochemical indicators of renal failure. Post-mortem examinations found extensive visceral gout in both vultures. Both control vultures survived without biochemical indicators of renal failure. With this evidence, we call for an immediate and comprehensive ban of nimesulide throughout South Asia to ensure the survival of the region's Critically Endangered vultures. More generally, testing the impacts of drugs on non-target species should be the responsibility of the pharmaceutical industry, before their veterinary use is licensed.

Spatiotemporal trends and annual fluxes of pharmaceuticals in a Scottish priority catchment.

Pharmaceuticals (a class of emerging contaminants) are continuously introduced into effluent-receiving surface waters due to their incomplete removal within wastewater treatment plants (WWTPs). This work investigated the presence and distribution of eight commonly used human pharmaceuticals in the River Dee (Scotland, UK), a Scottish Environment Protection Agency priority catchment that is a conservation site and important raw water source. Grab sampling and passive sampling (Polar Organic Chemical Integrative Sampler, POCIS) was performed over 12 months, targeting: paracetamol, ibuprofen, and diclofenac (analgesics/anti-inflammatories); clarithromycin and trimethoprim (antibiotics); carbamazepine and fluoxetine (psychoactive drugs); and 17α-ethynylestradiol (estrogen hormone). Sampling sites spanned from the river's rural source to the heavily urbanised estuary into the North Sea. Ibuprofen (ranging 0.8-697 ng/L), paracetamol (ranging 4-658 ng/L), trimethoprim (ranging 3-505 ng/L), diclofenac (ranging 2-324 ng/L) and carbamazepine (ranging 1-222 ng/L) were consistently detected at the highest concentrations through grab sampling, with concentrations generally increasing down river with increasing urbanisation. However, POCIS revealed trace contamination of most compounds throughout the river (commonly <0.5 ng/L), indicating pollution may be related to diffuse sources. Analysis of river flows revealed that low flow and warm seasons corresponded to statistically significantly higher concentrations of diclofenac and carbamazepine, two compounds of environmental and regulatory concern. Below the largest WWTP, annual average fluxes ranged 0.1 kg/yr (clarithromycin) to 143.8 kg/yr (paracetamol), with 226.2 kg/yr for total target compounds. It was estimated that this source contributed >70% of the total mass loads (dissolved phase) of the target compounds in the river. As the River Dee is an important raw water source and conservation site, additional catchment monitoring is warranted to safeguard water quality and assess environmental risk of emerging contaminants, particularly in relation to unusual weather patterns, climate change and population growth.

Trace element bioaccumulation in hypersaline ecosystems and implications of a global invasion.

Hypersaline ecosystems are under increasing threat due to anthropogenic pressures such as environmental pollution and biological invasions. Here we address the ecotoxicological implications of the Artemia franciscana (Crustacea) invasion in saltpans of southern Spain. This North American species is causing the extinction of native Artemia populations in many parts of the globe. The bioaccumulation of trace elements (As, Cd, Cu, Co, Cr, Mn, Ni, Pb and Zn) in native populations (A. parthenogenetica) from Cabo de Gata and Odiel saltpans and invasive Artemia from Cádiz saltpan was studied at different salinities. Furthermore, in Odiel, the most polluted study site, we also analysed the bioaccumulation of trace elements by Chironomus salinarius larvae (Diptera) and Ochthebius notabilis adults (Coleoptera). High levels of trace elements were detected in the studied saltpans, many of them exceeding the recommended threshold guidelines for aquatic life. Bioaccumulation of trace elements by Artemia was lowest at the highest salinity. The invasive A. franciscana showed higher potential to bioaccumulate trace elements than its native counterpart (in particular for As, Cd, Ni and Cr). In Odiel, O. notabilis stood out as showing the highest potential to bioaccumulate As and Cu. Results showed that the shift from a native to an alien Artemia species with a higher bioaccumulation capacity may increase the transfer of trace elements in hypersaline food webs, especially for waterbirds that depend on Artemia as food. Thus, our study identifies an indirect impact of the Artemia franciscana invasion that had not previously been recognised.

Increasing incidence of barbiturate intoxication in avian scavengers and mammals in Spain.

Pharmaceuticals are considered emerging contaminants in terms of impacts on wildlife. One chemical group of concern is euthanasia agents used in veterinary medicine. Here we present data on the occurrence of barbiturate intoxication using samples collected from 2004 to 2020 of suspected wildlife and domestic animal poisoning cases in Spain (n = 3210). Barbiturate intoxication was seen in 3.4% (45/1334) of the total number of confirmed intoxicated animals. Barbiturates were detected in 0.2% (1/448) of baits containing detectable poisons. The most frequently detected barbiturate was pentobarbital (42/45, 93.3%), but we also detected phenobarbital, barbital, and thiopental (2.2% prevalence for each). Avian scavengers were most frequently affected by barbiturate intoxication (n = 36), especially Eurasian griffon vultures (Gyps fulvus) (n = 28). Median pentobarbital concentrations detected in intoxicated griffon vultures was 27.3 mg kg-1 in gastric content and 38.1 mg kg-1 in liver, which highlights the acute effect of the chemical soon after ingestion. At least two large intoxication events affecting griffon vultures were related to the consumption of carcasses from euthanized livestock. We also found phenobarbital in a prepared bait linked to the intoxication of one Eurasian buzzard (Buteo buteo). This study highlights the need for stronger regulation of barbiturates to avoid secondary intoxications due to improper disposal of euthanized livestock.