The threat from ozone to vegetation in Ireland.

Ozone is the most damaging air pollutant to vegetation globally. Metrics of accumulated ozone above a concentration threshold (e.g. AOT40, ppb·h) have been widely used to assess ozone risk. However, there is growing consensus that accumulated Phytotoxic Ozone Dose (POD) above a receptor-specific critical stomatal flux threshold (y; nmol O3 m-2 s-1), expressed per unit of projected leaf area, provides a more reliable risk assessment, as it considers ozone entering the leaf (PODy, mmol m-2 leaf area). Few studies have assessed both concentration- and flux-based metrics using site-specific observations of ozone and meteorology. In this study we assessed the risk that ozone poses to five vegetation types across eight sites in Ireland during 2005-2021, using AOT40 and PODy risk metrics, and we predicted impacts using dose-response relationships. Long-term trends in both metrics were also assessed. The PODy critical level for vegetation protection was exceeded for all vegetation types, with exceedances most common at Atlantic coastal sites, and for tree species (beech POD1 15.7-25.7 mmol/m2 PLA). When PODy and AOT40 results were normalised based on their respective critical levels, predicted impacts were higher for PODy. There were significant increases in PODy for three vegetation types at rural sites during the study period, which also experienced increases in temperature and global solar radiation. The long-term trends were consistent with other European studies that show decreases in AOT40 and increases in PODy. While ozone concentrations in Ireland are relatively low (39-75 µg/m3 five-year average range), the humid climate and longer growing season may lead to elevated stomatal ozone uptake and thereby a risk to vegetation.

The Fate of Microplastics in Rural Headwater Lake Catchments.

In this study, the fluxes of microplastics (mp) were quantified during a 12-month period for three rural headwater lake catchments in Muskoka-Haliburton, south-central Ontario, Canada. A novel catchment particle balance approach was used, incorporating inputs from atmospheric deposition and stream inflows against lake outflow and sedimentation. This approach provides the first reported observation-based estimates of microplastic residence time in freshwater lakes. Atmospheric deposition had the highest daily microplastic flux (3.95-8.09 mp/m2/day), compared to the inflow streams (2.21-2.34 mp/m2/day), suggesting that it is the dominant source of microplastics to rural regions. Approximately 44-71% of the deposited microplastics were retained in the terrestrial catchments and 30-49% of the microplastics in the stream inflows were retained in the study lakes. Given that output fluxes ranged from 0.72-3.76 mp/m2/day in the sediment and 1.18-1.66 mp/m2/day in the lake outflows, the microplastic residence time was estimated to be between 3 and 12 years, suggesting that lakes are an important reservoir for microplastics. Fibers were the dominant shape in atmospheric deposition, streamwater, and lake water; however, in lake sediment, there was a higher proportion of fragments. Across all media, poly(ethylene terephthalate) was the dominant polymer identified (23%).

Robinia pseudoacacia L. (Black Locust) Leaflets as Biomonitors of Airborne Microplastics.

Here we investigate the suitability of Robinia pseudoacacia L. (black locust) leaflets as a novel biomonitor of airborne microplastics (MPs) including tyre wear particles (TWPs). Leaflets were collected from rural roadside locations (ROs, n = 5) and urban parks (UPs, n = 5) in Siena, Italy. MPs were removed by washing, identified by stereomicroscope, and analysed for polymer type by Fourier transform infrared spectroscopy. Daily MP deposition was estimated from leaf area. The mass magnetic susceptibility and the bioaccumulation of traffic-related potentially toxic elements (PTEs) were also analysed. The total number of MPs at ROs was significantly higher at 2962, dominated by TWPs, compared with 193 in UPs, where TWPs were not found. In contrast, total microfibres were significantly higher in UPs compared with ROs (185 vs. 86). Daily MP deposition was estimated to range from 4.2 to 5.1 MPs/m2/d across UPs and 29.9-457.6 MPs/m2/d across ROs. The polymer types at ROs were dominated by rubber (80%) from TWPs, followed by 15% polyamide (PA) and 5% polysulfone (PES), while in UPs the proportion of PES (44%) was higher than PA (22%) and polyacrylonitrile (11%). The mean mass magnetic susceptibility, a proxy of the bioaccumulation of traffic-related metallic particles, was higher at ROs (0.62 ± 0.01 10-8 m3/kg) than at UPs (-0.50 ± 0.03 10-8 m3/kg). The content of PTEs was similar across sites, except for significantly higher concentrations of Sb, a tracer of vehicle brake wear, at ROs (0.308 ± 0.008 µg/g) compared with UPs (0.054 ± 0.006 µg/g). Our results suggest that the waxy leaflets and easy determination of surface area make Robinia an effective biomonitor for airborne MPs including TWPs.

Soil carbon pools and fluxes following the regreening of a mining and smelting degraded landscape.

Increasing forest cover by regreening mining and smelting degraded landscapes provides an opportunity for global carbon (C) sequestration, however, the reported effects of regreening on soil C processes are mixed. One of the world's largest regreening programs is in the City of Greater Sudbury, Canada and has been ongoing since 1978. Prior to regreening, soils in the City of Greater Sudbury area were highly eroded, acidic, rich in metals, and poor in nutrients. This study used a chronosequence approach to investigate how forest soil C pools and fluxes have changed with stand age in highly "eroded" sites with minimal soil cover (n = 6) and "stable" sites covered by soil (n = 6). Encouragingly, the relationship between stand age and soil C processes (litterfall, litter decomposition, soil respiration, fine root growth) at both stable and eroded sites were comparable to observations reported for jack pine (Pinus banksiana Lamb.) and red pine (Pinus resinosa Ait.) plantations that have not been subject to over a century of industrial impacts. There was a strong "home-field advantage" for local decomposers, where litter decomposition rates were higher using a site-specific pine litter compared with a common pine litter. Higher soil respiration at eroded sites was linked to higher soil temperature, likely because of a more open tree canopy. Forest floor C pools increased with stand age while mineral soil C and aggregate C concentrations decreased with stand age. This loss of soil C is small relative to the substantial increases in aboveground tree and forest floor C pools, leading to a sizeable increase in total ecosystem C pools following regreening.

Effects of Shape and Size on Microplastic Atmospheric Settling Velocity.

Microplastics (MPs) have been found in all terrestrial, marine, and riparian environments, including remote regions. This implies that atmospheric transport is an important pathway when considering MP sources and global budgets. However, limited empirical data exist to aid in effective development and parameterization of MP atmospheric transport models. This study measured the atmospheric settling and horizontal drift velocities of various sizes and shapes of MPs in two specially designed settling columns using a laser Doppler anemometer. The settling velocities were generally lower than modeled values, while shape exerted the most significant influence on the rate of settling. Rather than conforming to well-established, power-law models, each class of MP exhibited a linear but different relationship between MP size and settling velocity, with markedly higher slopes for the spheres and cylinders as compared to the films and fibers. Shape also had a substantial influence on particle drift, with the fibers and films exhibiting the greatest horizontal motion, as suggestive of their changing orientation in response to particle interactions and fluid drag. As a consequence, microplastic particles identified within atmospheric deposition samples collected at a single point may derive from entirely different sources representing a wide range in transport distance.

Plastic debris in lakes and reservoirs.

Plastic debris is thought to be widespread in freshwater ecosystems globally1. However, a lack of comprehensive and comparable data makes rigorous assessment of its distribution challenging2,3. Here we present a standardized cross-national survey that assesses the abundance and type of plastic debris (>250 µm) in freshwater ecosystems. We sample surface waters of 38 lakes and reservoirs, distributed across gradients of geographical position and limnological attributes, with the aim to identify factors associated with an increased observation of plastics. We find plastic debris in all studied lakes and reservoirs, suggesting that these ecosystems play a key role in the plastic-pollution cycle. Our results indicate that two types of lakes are particularly vulnerable to plastic contamination: lakes and reservoirs in densely populated and urbanized areas and large lakes and reservoirs with elevated deposition areas, long water-retention times and high levels of anthropogenic influence. Plastic concentrations vary widely among lakes; in the most polluted, concentrations reach or even exceed those reported in the subtropical oceanic gyres, marine areas collecting large amounts of debris4. Our findings highlight the importance of including lakes and reservoirs when addressing plastic pollution, in the context of pollution management and for the continued provision of lake ecosystem services.

Moss Bags as Biomonitors of Atmospheric Microplastic Deposition in Urban Environments.

Microplastics (plastic particles <5 mm) were first identified in the environment during the 1970s and have since become ubiquitous across every environmental compartment. However, few studies have focused on atmospheric microplastics, and even fewer have used biological monitoring to assess their atmospheric deposition. Here, we assess the efficacy of moss bags as an active biomonitoring technique for atmospheric microplastic deposition. Moss (Pleurozium schreberi) bags were exposed in duplicate at nine deployment sites across a gradient of urban intensity in southern Ontario, Canada. A total of 186 microplastics (mp) were detected in the moss bags, resulting in a mean accumulation of 7.9 mp g-1 dry weight moss across all sites during the exposure period (45 days). The median microplastic length was 0.56 mm (range 0.03-4.51 mm), and the dominant microplastic type was fibres (47%), followed by fragments (39%). Microplastic accumulation significantly increased with urban intensity, ranging from 3.7 mp g-1 in low-density suburban areas to 10.7 mp g-1 in densely populated and trafficked urban areas. In contrast, microfibres by proportion dominated in suburban (62%) compared with urban areas (33%). Microplastic deposition was estimated to range from 21 to 60 mp m-2 day-1 across the nine deployment sites. The results suggest that moss bags may be a suitable technique for the active biomonitoring of atmospheric microplastic deposition in urban environments.

Compounds of wastewater origin in remote upland lakes in Ireland.

It is well established that persistent organic pollutants are transported long distances in the atmosphere and deposited into aquatic and terrestrial ecosystems in remote areas, including high altitude lakes. The objective of this research was to evaluate whether compounds of wastewater origin were present in four remote upland headwater lakes in Ireland that primarily receive loadings from atmospheric deposition. Using Polar Organic Chemical Integrative Samplers (POCIS) deployed in the lakes for 60 to 68 days, seven compounds were detected at levels that could be quantified but 25 of the target compounds were not detected. The detected compounds included the cannabinoid metabolite, tetrahydrocannabinol carboxylate (THC-COOH), codeine, acetaminophen (paracetamol), ibuprofen, and the artificial sweeteners, sucralose, and saccharin, which were all present at concentrations estimated to be < 125 ng/L. Caffeine was also present in the lakes at estimated concentrations between 213 and 1320 ng/L. Cocaine and tramadol were detected in POCIS deployed in some of the lakes, but at levels below the limits of quantitation. The highest concentrations of the target analytes were detected in two lakes located in the eastern part of Ireland. These data are consistent with regional atmospheric transport of these compounds originating from wastewater treatment plants in Ireland. However, contaminants from wastewater treatment plants in the United Kingdom may also be a source in these upland lakes that are located far from emissions of urban pollution.

Lichen Biomonitoring of Airborne Microplastics in Milan (N Italy).

This study investigated the deposition of airborne microplastics (MPs) in the urban area of Milan across 12 sites and at a background control site (northern Italy) using 3-month transplants of the fruticose lichen species Evernia prunastri (exposed in triplicate). The primary objective was to evaluate the use of lichen transplants for the assessment of MP deposition; as such, the study sites spanned a gradient in vehicular traffic and population density across four concentric land-use zones (i.e., urban parks, centre, semi-periphery, and periphery). A total of 149 MP particles were detected in the exposed lichen samples; 94.6% were classified as fibres and 5.4% as fragments. The control site and urban parks experienced a similar number of MPs per gram of dry lichen (20-26 MP/g), while a higher number of MPs were detected in central and peripheral areas (44-56 MP/g), with a clear increasing gradient from the city centre towards the periphery. We estimated the MP deposition in Milan to be in the range of 43-119 MPs m2/d, indicating that people living in Milan are exposed to airborne MPs, with potential health effects. This study suggests that lichens are suitable biomonitors of airborne MPs under a relatively short exposure of three months in urban environments.

Atmospheric deposition of anthropogenic particles and microplastics in south-central Ontario, Canada.

Microplastics are ubiquitous in the environment; however, few studies have examined their abundance in atmospheric deposition in pristine environments, remote from anthropogenic emission sources. In the current study, atmospheric deposition samples were collected for 13 months (February 2019-March 2020) from four precipitation chemistry monitoring stations located in Muskoka-Haliburton, south-central Ontario, Canada. Anthropogenic particles (i.e., synthetic particles but not necessarily plastic) were observed at each station with an average deposition rate of 57 particles/m2/day (range from 32 to 73 particles/m2/day). Of the anthropogenic particles identified, 12% were plastic resulting in an average microplastic (mp) deposition rate of 7 mp/m2/day (range 4-9 mp/m2/day). Approximately 85% of the particles were fibres with fragments comprising only 15%. The most common particle colours were blue and red with 50% of the fragments and 84% of fibres being one of these two colours. Raman spectroscopy determined that polyamide and polyethylene terephthalate were the two most abundant polymers at 24% and 19%, respectively. Across the four stations anthropogenic particle concentrations were significantly related to wind speed (rs = 0.32 to 0.62) and temperature (rs = -0.53 to -0.84), with a noticeable increase in particle concentration when wind shifted from the west (average of 7.2 mp/L) to the south-east (average of 11.5 mp/L). Faster wind speed resulted in a larger airshed source area, and the seasonal effect associated with changes in temperature and wind direction led to changes in potential source regions that were contributing microplastics, such as the Greater Toronto Area (>200 km away).

Ecological thresholds under atmospheric nitrogen deposition for 1200 herbaceous species and 24 communities across the United States.

Nitrogen (N) emissions and atmospheric deposition have increased significantly during the last century and become a stressor for many N-sensitive plant species. Understanding individual and community herbaceous plant species thresholds to atmospheric N deposition can inform emissions reduction policy. Here, we present results using Threshold Indicator Taxa Analysis (TITAN) applied to more than 1200 unique plant species and 24 vegetation communities (i.e., alliances) across the United States (US) to assess vulnerability to N deposition. Alliance-level thresholds (change points) for species decreasing in abundance along the gradient ranged from 1.8 to 14.3 kg N ha─1  year─1 and tended to be lower in the west than the east, which suggests that eastern communities, where N deposition has been historically higher, may have already lost many sensitive species. For the species that were present in more than one alliance, over half had a variable response to the N deposition gradient, suggesting that local factors affect vulnerability. Significant progress has been made during the past 30 years to reduce N emissions, which has reduced the percentage of plots at risk to N deposition from 72% to 35%. Nevertheless, over a third of plots remain at risk, and an average reduction of N deposition of 20% would protect half of the plots where N deposition exceeds community thresholds. Furthermore, the alliance- and species-level change points determined in this study may be used to inform N critical loads.

Dissolved Organic Carbon in Lakes of the Athabasca Oil Sands Region: Is Color an Indicator of Acid Sensitivity?

The Athabasca oil sands region (AOSR) in north-eastern Alberta, Canada, contains the world's third largest known bitumen deposit. Oil sands (OS) operations produce emissions known to contribute to acidic and alkaline deposition, which can alter the chemistry of the receiving surface waters, including dissolved organic carbon (DOC). Little is known regarding the natural variability of aquatic DOC among lakes within the AOSR. Surface-water data from 50 lakes were analyzed; variables known to be associated with the light-absorptive properties of DOC (true color [TC]) were evaluated to investigate the potential variability of chromophoric DOC (CDOC). Comparison of TC and DOC revealed two distinct "high" (H) and "low" (L) lake subpopulations, the former being characterized by high relative TC and low DOC, and the latter by the inverse. The H lakes were defined by variables known to be associated with CDOC, while L lakes appeared well-buffered potentially owing to groundwater inputs. The divergent optical properties between subpopulations appeared partially attributable to pH-limited Fe complexation. Trajectory analysis indicated that H lakes most likely to receive atmospheric deposition from OS sources experienced significantly lower pH. These results are contrary to previous studies that found OS emissions to have minimal acidifying effect over lakes throughout the AOSR.

Accumulation of airborne microplastics in lichens from a landfill dumping site (Italy).

The aim of this study was to assess if lichens (Flavoparmelia caperata) surrounding a landfill dumping site in Italy accumulated higher amounts of microplastics compared with lichens at more distant sites. Lichen samples were collected at three sites along a transect from the landfill: close (directly facing the landfill), intermediate (200 m), and remote (1500 m). Anthropogenic microparticles (fibres and fragments) were determined visually after wet peroxide digestion of the samples, and microplastics were identified based on a hot needle test; the type of plastic was identified by micro-Raman analysis. The results showed that lichens collected in the vicinity of the landfill accumulated the highest number of anthropogenic microfibres and fragments (147 mp/g dw), and consequently microplastics (79 mp/g dw), suggesting that the impact of landfill emissions is spatially limited. The proportion of fibres and fragments identified as microplastics was 40% across all sites and the most abundant polymer type was polyester or polyethylene terephthalate (68%). These results clearly indicated that lichens can effectively be used to monitor the deposition of microplastics.

Decadal Changes in Trace Metal Concentrations in Upland Headwater Lakes.

The objective of this study was to assess the current chemistry of trace elements in upland headwater lakes in Ireland and determine their trends during the last decade in response to decreasing emissions. Twenty-nine upland lakes were sampled in 2017-2018; 19 were previously sampled in 2007-2008. The 2017-2018 samples were analyzed for conductivity, pH, DOC, and 18 trace elements. The lakes had low element concentrations; only 7 of 18 trace elements were > 1 µg/L (Fe, Al, Zn, Mn, B, Sr and Ba). Nine elements were assessed for significant decadal changes; four elements decreased (B, Co, Mn, and Sr) and one increased (Pb). Their correlation with conductivity, pH, and DOC and the associated changes in those variables partially explained the observed trends. In general, elements that were correlated with DOC did not decrease, while those that were not correlated decreased between the two periods. Despite decreased anthropogenic emissions, ecosystem recovery and climate perturbations can confound or mask the benefits of emissions reductions.

Ambient Atmospheric Deposition of Anthropogenic Microfibers and Microplastics on the Western Periphery of Europe (Ireland).

Microfibers (mf) are the most common type of microplastic in the environment. Few studies have focused on their abundance in atmospheric deposition in background environments. In the current study, we collected wet-only and bulk rainfall from four precipitation chemistry monitoring stations, primarily located in coastal areas around Ireland. Anthropogenic mf were observed in all samples; the average deposition across the four study sites was 80 mf m-2 day-1. Wet-only mf deposition was 70 mf m-2 day-1 compared with bulk deposition of 100 mf m-2 day-1. The wet-only collectors were estimated to capture ∼70% of the bulk collectors, suggesting that dry deposition makes up at least 30% of total deposition. Meteorological variables, i.e., relative humidity, rainfall volume, wind speed, and wind direction, were significantly related to mf abundance, suggesting that rainfall washout and air mass movement are important predictors of mf deposition in background regions. In total, 15% of all anthropogenic mf were identified as plastic. The most abundant polymer type was polyester or polyethylene terephthalate at 71%, followed by polyacrylonitrile at 11%, polyethylene at 11%, and polypropylene at 4%. The average deposition of plastic mf was 12 mf m-2 day-1.

Moss as a biomonitor for the atmospheric deposition of anthropogenic microfibres.

Microplastics, which are plastic particles < 5 mm, have been found throughout the environment. However, few studies have focused on their transport via atmospheric deposition. Bryophytes have been used as biomonitors for the atmospheric deposition of trace elements, persistent organic pollutants and particulate matter, and may potentially be used to monitor the atmospheric deposition of microplastics or anthropogenic microfibres (mf). Hylocomium splendens was collected from three lake catchments, which are remote from anthropogenic disturbance and emissions sources. Anthropogenic mf were observed in all moss samples; the average number was 24 mf g-1 dry weight (range: 15-30 mf g-1) across the three study sites. The average length of mf was 1.02 mm (range: 0.83-1.20 mm). Plastic mf were identified using five rigorous visual criteria; 27% of the observed mf passed four criteria and 13% passed all five, suggesting at most a quarter of the mf may be plastic. Annual average atmospheric deposition of anthropogenic mf across the three lake catchments was estimated at ~47,700 mf m-2 (~12,000 plastic mf m-2), based on a moss biomass of 2 kg dry weight m-2. These preliminary findings suggest that moss may be a useful biomonitor for the atmospheric deposition of mf (and microplastics).

Interspecies comparison of three moss species (Hylocomium splendens, Pleurozium schreberi, and Isothecium stoloniferum) as biomonitors of trace element deposition.

Biomonitoring with mosses is a common method widely used to assess the spatial and temporal trends of atmospheric deposition in Europe since its introduction in the 1970s. Based on previous investigations, certain moss species provide the most accurate reflection of atmospheric deposition. However, sampling of just one species across large areas can pose a challenge, therefore the ability to use multiple moss species interchangeably is integral to an effective moss biomonitoring survey. In this study, biomonitoring abilities of two common species (Hylocomium splendens [Hs] and Pleurozium schreberi [Ps]) were compared to a potential new biomonitoring species endemic to North America (Isothecium stoloniferum [Is]). Thirteen metal concentrations were analyzed (Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Cd, and Pb) in moss tissue from 20 sites with co-located species (Ps/Hs, Is/Hs) Five metals (Al, V, Fe, Ni, and Pb) showed significant and strong correlations (Spearman correlation, r ≥ 0.7 α = 0.05) for all three species, reflecting the established deposition gradient in the region. Furthermore, there was no significant difference in observations (and moderate correlation) for Cr, which suggests that all species exhibited similar uptake abilities for these six metals (Al, V, Cr, Fe, Ni, and Pb). Four metals (Co, As, Se, and Cd) exhibited concentrations below detection at a number of sites, which may have influenced the assessment of interspecies relationships. It is recommended that interspecies calibration be carried out under all surveys that employ multiple moss species.

Dynamic Modeling and Target Loads of Sulfur and Nitrogen for Surface Waters in Finland, Norway, Sweden, and the United Kingdom.

The target load concept is an extension of the critical load concept of air pollution inputs to ecosystems. The advantage of target loads over critical loads is that one can define the deposition and the point in time (target year) when the critical (chemical) limit is no longer violated. This information on the timing of recovery requires dynamic modeling. Using a well-documented dynamic model, target loads for acidic deposition were determined for 848 surface waters across Finland, Norway, Sweden, and the United Kingdom for the target year 2050. In the majority of sites ( n = 675), the critical ANC-limit was predicted to be achieved by 2050; however, for 127 sites, target loads were determined. In addition, 46 sites were infeasible, i.e., even a reduction of anthropogenic deposition to zero would not achieve the limit by 2050. The average maximum target load for sulfur was 38% lower than the respective critical load across the study lakes ( n = 127). Target loads on a large regional scale can inform effects-based emission reduction policies; the current assessment suggests that reductions beyond the Gothenburg Protocol are required to ensure surface water recovery from acidification by 2050.

Critical loads of acidity and exceedances for 1138 lakes and ponds in the Canadian Arctic.

Sulphur emissions associated with increased anthropogenic activity, such as resource extraction and marine shipping, may lead to the acidification of aquatic freshwater systems in the Arctic. In the current study, acid sensitivity (based on a critical load (CL(Ac)) approach) of 1138 lakes and ponds in the Canadian Arctic was quantified using the Steady-State Water Chemistry (SSWC) model. Ecosystem protection was based on an Acid Neutralising Capacity limit (ANClimit) for Arctic Char. Acidification risk was estimated under modelled sulphur deposition for the year 2010 (two scenarios). Overall, surface water CL(Ac) values for the Canadian Arctic were low (median = 35.8 meq·m-2·yr-1, mean = 96.3 meq·m-2·yr-1), with approximately 40% (n = 455) of sites estimated to be sensitive to acidification (CL(Ac) < 20 meq·m-2·yr-1). Higher CL(Ac) values were found in Yukon (434.5 meq·m-2·yr-1, n = 40), Ellesmere Is. (262.2 meq·m-2·yr-1, n = 143), and Southampton Is. (251.5 meq·m-2·yr-1, n = 35), while lower CL(Ac) values were found in Melville Is. (5.5 meq·m-2·yr-1, n = 48), Banks Is. (18.4 meq·m-2·yr-1, n = 45), and Bylot Is. (20.4 meq·m-2·yr-1, n = 36). Under modelled deposition for 2010, 12-12.5% (n = 136-142) of all sites were exceeded. The highest proportion of exceeded sites were observed in Ellef Ringnes Is. (48-60%; n = 12-15), Melville Is. (38-44%; n = 18-21), and Northwest Territories (24-26%; n = 23-26).