Pulmonary toxicity of synthetic amorphous silica - effects of porosity and copper oxide doping.

Materials can be modified for improved functionality. Our aim was to test whether pulmonary toxicity of silica nanomaterials is increased by the introduction of: a) porosity; and b) surface doping with CuO; and whether c) these modifications act synergistically. Mice were exposed by intratracheal instillation and for some doses also oropharyngeal aspiration to: 1) solid silica 100 nm; 2) porous silica 100 nm; 3) porous silica 100 nm with CuO doping; 4) solid silica 300 nm; 5) porous silica 300 nm; 6) solid silica 300 nm with CuO doping; 7) porous silica 300 nm with CuO doping; 8) CuO nanoparticles 9.8 nm; or 9) carbon black Printex 90 as benchmark. Based on a pilot study, dose levels were between 0.5 and 162 µg/mouse (0.2 and 8.1 mg/kg bw). Endpoints included pulmonary inflammation (neutrophil numbers in bronchoalveolar fluid), acute phase response, histopathology, and genotoxicity assessed by the comet assay, micronucleus test, and the gamma-H2AX assay. The porous silica materials induced greater pulmonary inflammation than their solid counterparts. A similar pattern was seen for acute phase response induction and histologic changes. This could be explained by a higher specific surface area per mass unit for the most toxic particles. CuO doping further increased the acute phase response normalized according to the deposited surface area. We identified no consistent evidence of synergism between surface area and CuO doping. In conclusion, porosity and CuO doping each increased the toxicity of silica nanomaterials and there was no indication of synergy when the modifications co-occurred.

Concentration and origin of lead (Pb) in liver and bone of Eurasian buzzards (Buteo buteo) in the United Kingdom.

Ingestion of lead (Pb) derived from ammunition used in the hunting of game animals is recognised to be a significant potential source of Pb exposure of wild birds, including birds of prey. However, there are only limited data for birds of prey in Europe regarding tissue concentrations and origins of Pb. Eurasian buzzards (Buteo buteo) found dead in the United Kingdom during an 11-year period were collected and the concentrations of Pb in the liver and femur were measured. Concentrations in the liver consistent with acute exposure to Pb were found in 2.7% of birds and concentration in the femur consistent with exposure to lethal levels were found in 4.0% of individuals. Pb concentration in the femur showed no evidence of consistent variation among or within years, but was greater for old than for young birds. The Pb concentration in the liver showed no effect of the birds' age, but varied markedly among years and showed a consistent tendency to increase substantially within years throughout the UK hunting season for gamebirds. The resemblance of the stable isotope composition of Pb from buzzard livers to that of Pb from the types of shotgun ammunition most widely-used in the UK increased markedly with increasing Pb concentration in the liver. Stable isotope results were consistent with 57% of the mass of Pb in livers of all of the buzzards sampled being derived from shotgun pellets, with this proportion being 89% for the birds with concentrations indicating acute exposure to Pb. Hence, most of the Pb acquired by Eurasian buzzards which have liver concentrations likely to be associated with lethal and sublethal effects is probably obtained when they prey upon or scavenge gamebirds and mammals shot using Pb shotgun pellets.

Biological and anthropogenic predictors of metal concentration in the Eurasian otter, a sentinel of freshwater ecosystems.

Toxic metals have been linked to a range of adverse health effects in freshwater organisms. However, for higher vertebrates, there is little understanding of the large-scale drivers of exposure. We quantified toxic metal/semi-metal concentrations in a sentinel freshwater top predator, the Eurasian otter (Lutra lutra), across England and Wales, and determined how this varied with key natural and anthropogenic factors. We related liver concentrations in 278 otters that died between 2006 and 2017 to habitat biogeochemistry, proximity to point source contamination and to biological characteristics (length, sex, condition). Evidence for any positive association with putative anthropogenic sources (mining, human population, known discharges) was weak or lacking in nearly all cases, with the exception of a positive association between lead and human population density. Despite concerns that burgeoning use of nanosilver in consumer products might increase silver concentrations in waste waters, there was no increase over time. Spatial variation in soil/sediment pH, precipitation, and soil calcium oxide are indicated as significant predictors of metal concentrations in otters (higher cadmium and silver in areas with lower pH and higher rainfall, and higher chromium and lead in areas of lower calcium oxide). Liver chromium and nickel concentrations declined significantly over time (Cr 0.030 ± 1.2 to 0.015 ± 1.3 µg/g dry weight, Ni 0.0038 ± 1.2 to 0.00068 ± 1.5 µg/g, between 2006-2009 and 2014-2017), but other metals showed no temporal change. Biotic associations were important, with age related accumulation indicated for mercury and cadmium (as well as interactions with body condition). Our results suggest that larger-scale geochemical and hydrological processes are important in determining metal exposure in otters, and we provide an indication of risk factors that may be of relevance for freshwater vertebrates in other countries with well-developed water pollution management.

Interactions between Environmental Contaminants and Gastrointestinal Parasites: Novel Insights from an Integrative Approach in a Marine Predator.

Environmental contaminants and parasites are ubiquitous stressors that can affect animal physiology and derive from similar dietary sources (co-exposure). To unravel their interactions in wildlife, it is thus essential to quantify their concurring drivers. Here, the relationship between blood contaminant residues (11 trace elements and 17 perfluoroalkyl substances) and nonlethally quantified gastrointestinal parasite loads was tested while accounting for intrinsic (sex, age, and mass) and extrinsic factors (trophic ecology inferred from stable isotope analyses and biologging) in European shags Phalacrocorax aristotelis. Shags had high mercury (range 0.65-3.21 µg g-1 wet weight, ww) and extremely high perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) residues (3.46-53 and 4.48-44 ng g-1 ww, respectively). Males had higher concentrations of arsenic, mercury, PFOA, and PFNA than females, while the opposite was true for selenium, perfluorododecanoic acid (PFDoA), and perfluooctane sulfonic acid (PFOS). Individual parasite loads (Contracaecum rudolphii) were higher in males than in females. Females targeted pelagic-feeding prey, while males relied on both pelagic- and benthic-feeding organisms. Parasite loads were not related to trophic ecology in either sex, suggesting no substantial dietary co-exposure with contaminants. In females, parasite loads increased strongly with decreasing selenium:mercury molar ratios. Females may be more susceptible to the interactive effects of contaminants and parasites on physiology, with potential fitness consequences.

Consistency and uncertainty of UK measurements of mercury in precipitation.

A novel method to assess the uncertainty of measurement of mercury in precipitation for the UK's Heavy Metals Monitoring Network is presented. The method makes use of the fact that, because of the high risk of sample contamination, samples are taken in duplicate in order to ensure valid data is available for as many sampling periods as possible. Where both samples are valid a good opportunity is afforded to use the statistical differences in the rain volumes sampled and the mercury concentrations measured to assess the overall uncertainty of the measurement. This process has produced estimated uncertainties in good agreement with previous studies and well within the limits specified by European legislation. The work also highlighted an effective method to spot outliers in the paired samples at the data ratification stage.

An analysis of benign human prostate offers insights into the mechanism of apocrine secretion and the origin of prostasomes.

The structure and function of normal human prostate is still not fully understood. Herein, we concentrate on the different cell types present in normal prostate, describing some previously unreported types and provide evidence that prostasomes are primarily produced by apocrine secretion. Patients (n = 10) undergoing TURP were prospectively consented based on their having a low risk of harbouring CaP. Scanning electron microscopy and transmission electron microscopy was used to characterise cell types and modes of secretion. Zinc levels were determined using Inductively Coupled Plasma Mass Spectrometry. Although merocrine secretory cells were noted, the majority of secretory cells appear to be apocrine; for the first time, we clearly show high-resolution images of the stages of aposome secretion in human prostate. We also report a previously undescribed type of epithelial cell and the first ultrastructural image of wrapping cells in human prostate stroma. The zinc levels in the tissues examined were uniformly high and X-ray microanalysis detected zinc in merocrine cells but not in prostasomes. We conclude that a significant proportion of prostasomes, possibly the majority, are generated via apocrine secretion. This finding provides an explanation as to why so many large proteins, without a signal peptide sequence, are present in the prostatic fluid.

Temporal and Spatial Distribution of Mercury in Gulls Eggs from the Iberian Peninsula.

We examined how coastal mercury contamination varied spatially and temporally across the Iberian Peninsula by measuring mercury concentrations in the eggs of the sentinel biomonitor yellow-legged gull (Larus michahellis). Samples were collected from eight colonies that ranged from the Atlantic across the south and northern areas of the Mediterranean. We also measured Hg residues in eggs of the one of the most endangered gull species in the world, the Audouin's gull (Larus audouinii) from the Ebro Delta, where colonies of yellow-legged and Audouin's gull co-occur. Fresh eggs were collected in 2009 and 2016 and samples were pooled from each colony for analysis. Mercury concentrations in yellow-legged gulls ranged between 0.4 and 2.8 mg/kg dry weight (dw); although there were no significant differences in concentrations between sampling periods, significant differences were found between colonies. Higher concentrations were associated with northern Mediterranean colonies (Columbretes and Ebro Delta), likely due to proximity to emission sources, circulatory marine currents and diet composition. Mercury concentrations in yellow-legged gull eggs were lower than those reported to result in impaired hatching. Residues in Audouin's gull eggs from the Ebro Delta were significantly higher (4.0-5.6 mg/kg dw) than those in yellow-legged gull from the same location, probably associated with dietary differences. Mercury levels in Audouin's gull were ten times above the benchmark suggested to reduce nest success by 10%. Overall, these results raise concern for adverse health impacts in this protected seabird species and further investigation in Audouin's gull eggs from the Ebro Delta is recommended.

Influence of soil porewater properties on the fate and toxicity of silver nanoparticles to Caenorhabditis elegans.

Engineered nanoparticles (NPs) entering the environment are subject to various transformations that in turn influence how particles are presented to, and taken up by, organisms. To understand the effect of soil properties on the toxicity of nanosilver to Caenorhabditis elegans, toxicity assays were performed in porewater extracts from natural soils with varying organic matter content and pH using 3-8 nm unfunctionalized silver (Ag 3-8Unf), 52-nm polyvinylpyrrolidone (PVP)-coated Ag NPs (Ag 52PVP), and AgNO3 as ionic Ag. Effects on NP agglomeration and stability were investigated using ultraviolet-visible (UV-vis) spectroscopy and asymmetric flow field-flow fractionation (AF4); Ag+ showed greater overall toxicity than nanosilver, with little difference between the NP types. Increasing soil organic matter content significantly decreased the toxicity of Ag 3-8Unf, whereas it increased that of AgNO3 . The toxicity of all Ag treatments significantly decreased with increasing porewater pH. Dissolution of both NPs in the porewater extracts was too low to have contributed to their observed toxic effects. The UV-vis spectroscopy revealed low levels of agglomeration/aggregation independent of soil properties for Ag 3-8Unf, whereas higher organic matter as well as low pH appeared to stabilize Ag 52PVP. Overall, both soil organic matter content and pH affected NP fate as well as toxicity to C. elegans; however, there appears to be no clear connection between the measured particle characteristics and their effect. Environ Toxicol Chem 2018;37:2609-2618. © 2018 SETAC.

Particulate and colloidal silver in sewage effluent and sludge discharged from British wastewater treatment plants.

Differential filtration was used to measure silver (>2 nm) entering and leaving nine sewage treatment plants (STPs). The mean concentration of colloidal (2-450 nm) silver, which includes nanosilver, was found to be 12 ng L(-1) in the influent and 6 ng L(-1) in the effluent. For particulate silver (>450 nm) the mean values were 3.3 µg L(-1) for influent and 0.08 µg L(-1) for effluent. Thus, removal was around 50% and 98% for colloidal and particulate silver respectively. There was no significant difference in performance between the different types of STP investigated (three examples each of activated sludge, biological filter and biological filter with tertiary treatment located across England, UK). In addition, treated sewage sludge samples (biosolids) were taken from several STPs to measure the total silver likely to be discharged to soils. Total silver was 3-14 mg kg(-1) DW in the sludge (median 3.6), which if the sludge were added at the recommended rate to soil, would add 11 µg kg(-1) yr(-1) to the top 20 cm soil layer. Predicted concentrations using the LF2000-WQX model for all the rivers of England and Wales for nanosilver were typically in the 0-1 ng L(-1) range but levels up to 4 ng L(-1) are possible in a high discharge and low flow scenario. Predicted concentrations for the total particulate forms were mostly below 50 ng L(-1) except for a high discharge and low flow scenario where concentrations could reach 135 ng L(-1).

Phosphorus retention and remobilization along hydrological pathways in karst terrain.

Karst landscapes are often perceived as highly vulnerable to agricultural phosphorus (P) loss, via solution-enlarged conduits that bypass P retention processes. Although attenuation of P concentrations has been widely reported within karst drainage, the extent to which this results from hydrological dilution, rather than P retention, is poorly understood. This is of strategic importance for understanding the resilience of karst landscapes to P inputs, given increasing pressures for intensified agricultural production. Here hydrochemical tracers were used to account for dilution of P, and to quantify net P retention, along transport pathways between agricultural fields and emergent springs, for the karst of the Ozark Plateau, midcontinent USA. Up to ∼ 70% of the annual total P flux and ∼ 90% of the annual soluble reactive P flux was retained, with preferential retention of the most bioavailable (soluble reactive) P fractions. Our results suggest that, in some cases, karst drainage may provide a greater P sink than previously considered. However, the subsequent remobilization and release of the retained P may become a long-term source of slowly released "legacy" P to surface waters.

Earthworms produce phytochelatins in response to arsenic.

Phytochelatins are small cysteine-rich non-ribosomal peptides that chelate soft metal and metalloid ions, such as cadmium and arsenic. They are widely produced by plants and microbes; phytochelatin synthase genes are also present in animal species from several different phyla, but there is still little known about whether these genes are functional in animals, and if so, whether they are metal-responsive. We analysed phytochelatin production by direct chemical analysis in Lumbricus rubellus earthworms exposed to arsenic for a 28 day period, and found that arsenic clearly induced phytochelatin production in a dose-dependent manner. It was necessary to measure the phytochelatin metabolite concentrations directly, as there was no upregulation of phytochelatin synthase gene expression after 28 days: phytochelatin synthesis appears not to be transcriptionally regulated in animals. A further untargetted metabolomic analysis also found changes in metabolites associated with the transsulfuration pathway, which channels sulfur flux from methionine for phytochelatin synthesis. There was no evidence of biological transformation of arsenic (e.g. into methylated species) as a result of laboratory arsenic exposure. Finally, we compared wild populations of earthworms sampled from the field, and found that both arsenic-contaminated and cadmium-contaminated mine site worms had elevated phytochelatin concentrations.

The presence of EU priority substances mercury, hexachlorobenzene, hexachlorobutadiene and PBDEs in wild fish from four English rivers.

Since 2007 about 200 to 300 fish per year--generally roach (Rutilus rutilus) also a few bleak (Alburnus alburnus) and eels (Anguilla anguilla)--have been collected from a number of English river sites and stored at -80°C to build up a Fish Tissue Archive as a resource for the monitoring of pollutants. Some of the fish from the Fish Tissue Archive from the years 2007-2011 were analyzed for substances in current and proposed European legislation regarding environmental quality standards (EQS) in biota. It was found that mercury exceeded the EU EQS of 20 µg/kg in 79% of samples with an average and median of 31 and 29 µg/kg. The legacy fungicide hexachlorobenzene (HCB) was below the EQS of 10 µg/kg in all fish analyzed, with a maximum of 6 µg/kg in some eels. The legacy solvent hexachlorobutadiene (HCBD) was below the EQS of 55 µg/kg, being <0.2 µg/kg in all samples where it was measured. The sums of six polybrominated diphenyl ethers (PBDEs) were several orders of magnitude higher than the new proposed 0.0085 µg/kg biota EQS. This study showed that the regular collection and analysis of whole body homogenate samples of relatively small native pelagic fish is suitable for the monitoring of contaminants capable of bioaccumulation. With regard to current or proposed EQS for EU countries, mercury and potentially PBDE in fish are of some concern in these English rivers.

An intermediate complexity dynamic model for predicting accumulation of atmospherically-deposited metals (Ni, Cu, Zn, Cd, Pb) in catchment soils: 1400 to present.

The Intermediate Dynamic Model for Metals (IDMM) is a model for prediction of the pools of metals (Ni, Cu, Zn, Cd, Pb) in topsoils of catchments resulting from deposition of metals from the atmosphere. We used the model to simulate soil metal pools from 1400 onwards in ten UK catchments comprising semi-natural habitats, and compared the results with present day observations of soil metal pools. Generally the model performed well in simulating present day pools, and further improvements were made to simulations of Ni, Cu, Zn and Cd by adjusting the strength of metal adsorption to the soils. Some discrepancies between observation and prediction for Pb appeared to be due either to underestimation of cumulative deposition, or to overestimation of the metal pool under 'pristine', pre-industrial conditions. The IDMM provides a potential basis for large scale assessment of metal dynamics in topsoils.

High-frequency water quality time series in precipitation and streamflow: from fragmentary signals to scientific challenge.

Eighteen months of 7-hourly analyses of rainfall and stream water chemistry are presented, spanning a wide range of chemical determinands and building on over 20 years of weekly records for the moorland headwaters of the river Severn. The high-frequency time series data show that hydrochemical responses to major hydrological and biological drivers of short-term variability in rainfall and rivers are not captured by conventional low-frequency monitoring programmes. A wealth of flow related, flow independent, diurnal, seasonal and annual fluctuations indicate a cacophony of interactions within the catchment and stream. The complexity of the chemical dynamics is visually obvious, although there appears to be no clear way of translating this complexity into a simple algorithm. The work provides a proof of concept for the complex structure of catchment functioning revealed by extensive high-frequency measurements coupled with high analytical sensitivity and reproducibility. It provides new insights into hydrogeochemical functioning and a novel resource for catchment modelling.

Outdoor and indoor cadmium distributions near an abandoned smelting works and their relations to human exposure.

The relationship of measured or modelled Cd concentrations in soil, house dust and available to plants with human urinary Cd concentrations were assessed in a population living around a Cd/Pb/Zn smelter in the UK. Modelled air concentrations explained 35% of soil Cd variation indicating the smelter contributed to soil Cd loads. Multi-variate analysis confirmed a significant role of biological and life-style factors in determining urinary Cd levels. Significant correlations of urinary Cd with soil, house dust and modelled plant available Cd concentrations were not, however, found. Potential reasons for the absence of clear relationships include limited environmental contact in urban populations; the role of undefined factors in determining exposure; and the limited spatial scope of the survey which did not sample from the full pollution gradient. Further, the absence of any significant relationship indicates that environmental measures provide limited advantage over atmospheric model outputs for first stage human exposure assessment.

Aluminium in UK rivers: a need for integrated research related to kinetic factors, colloidal transport, carbon and habitat.

Dissolved aluminium concentrations ([Al]) in the <0.45 µm filtered fraction are described for 54 UK river sites covering rural, acidic/acid sensitive, agricultural and urban typologies, and wide pH range (4 to 11). High [Al] occurred under acidic conditions and for acid runoff neutralised by bicarbonate rich groundwater. Thermodynamic analysis indicates Al hydroxide/hydroxy-silicate oversaturation at circumneutral pH across the rivers, but undersaturation at lower/higher pH. The oversaturation reflects in part the presence of Al bearing colloids as indicated by (1) [Al] being correlated with components associated with both lithogenic (Fe, Ti and lanthanides) colloids and organic carbon, (2) baseflow studies using cross-flow ultrafiltration and (3) comparison of our data with Acid Waters Monitoring Network (AWMN) information on labile and non-labile Al. Tree harvesting and emission reductions of SO(x) in acidic and acid sensitive catchments in mid-Wales led to acidification reversal, lower [Al] and changing [H(+)] - [Al] relationships. The [Al] decline was confined to acidic conditions while [Al] increased during the later part of the monitoring period with a peak around 2002 for moorland and forested systems. Colloidal production across the flow range was indicated late in the record by comparison of our data with information collected by the AWMN for a site in mid-Wales. This production seems interlinked with organic carbon and with dissolved CO(2) changes. In order for further understanding of Al hydrogeochemistry in river systems there is a need to integrate research that moves from equilibrium to kinetic and colloidal consideration including the critical issues of organic and inorganic controls within the context of bioavailability and aquatic stress. The colloidal Al may well be of low environmental concern to fish and other factors such as habitat may well be critical.

An assessment of the fate, behaviour and environmental risk associated with sunscreen TiO2 nanoparticles in UK field scenarios.

The fate of Ti was examined in an activated sludge plant serving over 200,000 people. These studies revealed a decrease of 30 to 3.2 µg/L of Ti < 0.45 µm from influent to effluent and a calculated Ti presence of 305 mg/kg DW in wasted sludge. Thus, using sludge as a fertiliser would result in a predicted deposition of up to 250 mg/m² of Ti to soil surfaces using a recommended maximal agricultural application rate. Given the major use of TiO2 in many industrial and domestic applications where loss to the sewer is possible, this measured Ti was presumed to have been largely TiO2, a proportion of which will be nanoparticle sized. To assess the behaviour of engineered nanoparticle (ENP) TiO2 in sewage and toxicology studies, Optisol (Oxonica Materials Ltd) and P25 (Evonik Industries AG), which are representative of forms used in sunscreen and cosmetic products, were used. These revealed a close association of TiO2 ENPs with activated sludge. Using commercial information on consumption, and removal rates for sewage treatment, predictions were made for river water concentrations for sunscreen TiO2 ENPs for the Anglian and Thames regions in Southern England. The highest predicted value from these exercises was 8.8 µg/L for the Thames region in which it was assumed that one in four people used the recommended application of sunscreen during a low flow (Q95) period. Ecotoxicological studies using potentially vulnerable species indicated that 1000 µg/L TiO2 ENP did not affect the viability of a mixed community of river bacteria in the presence of UV light. Direct exposure to TiO2 ENPs did not impair the immuno-effectiveness of earthworm coelomocyte cells at concentrations greatly above those predicted for sewage sludge.

Comparative chronic toxicity of nanoparticulate and ionic zinc to the earthworm Eisenia veneta in a soil matrix.

Manufactured nanoparticles (NPs) are increasingly being used in a range of consumer products and are already entering the environment. NP ZnO is one of the most widely used and potentially toxic NPs in aquatic exposures. It is likely that ZnO nanoparticles will also be bioavailable to soil organisms, studies on ZnO NP toxicity in a soil matrix are lacking. We exposed the earthworm Eisenia veneta to uncoated NP ZnO (<100 nm) dosed to soil and food at 250 and 750 mg Zn kg(-1) for 21 d. Concurrent exposures of equivalent ionic Zn were conducted with ZnCl(2) and for both forms effects on life history traits, immune activity and Zn body concentrations were compared. Despite slightly higher measured body concentrations, NP ZnO generally had less impact than ZnCl(2) on measured traits. At 750 mg Zn kg(-1), reproduction declined by 50% when exposed to NP ZnO but was almost completely inhibited by ZnCl(2). Similarly, immune activity was unaffected by NP ZnO but was suppressed by 20% when exposed to ZnCl(2). Scanning electron microscopy analysis of worm tissues following 24h aqueous exposure showed the presence of ZnO particles suggesting that NPs can be taken up in particulate form. This may explain the reduced effects at similar body concentrations seen in the soil study. Our findings suggest that risk assessments do not need to go beyond considering the metal component of NP ZnO in soils at least for the larger size uncoated particles considered here.

Hydrology and water quality of the headwaters of the River Severn: Stream acidity recovery and interactions with plantation forestry under an improving pollution climate.

This paper presents new information on the hydrology and water quality of the eroding peatland headwaters of the River Severn in mid-Wales and links it to the impact of plantation conifer forestry further down the catchment. The Upper Hafren is dominated by low-growing peatland vegetation, with an average annual precipitation of around 2650 mm with around 250 mm evaporation. With low catchment permeability, stream response to rainfall is "flashy" with the rising limb to peak stormflow typically under an hour. The water quality is characteristically "dilute"; stormflow is acidic and enriched in aluminium and iron from the acid organic soil inputs. Baseflow is circum-neutral and calcium and bicarbonate bearing due to the inputs of groundwater enriched from weathering of the underlying rocks. Annual cycling is observed for the nutrients reflecting uptake and decomposition processes linked to the vegetation and for arsenic implying seasonal water-logging within the peat soils and underlying glacial drift. Over the decadal scale, sulphate and nitrate concentrations have declined while Gran alkalinity, dissolved organic carbon and iron have increased, indicating a reduction in stream acidification. Within the forested areas the water quality is slightly more concentrated and acidic, transgressing the boundary for acid neutralisation capacity as a threshold for biological damage. Annual sulphate and aluminium concentrations are double those observed in the Upper Hafren, reflecting the influence of forestry and the greater ability of trees to scavenge pollutant inputs from gaseous and mist/cloud-water sources compared to short vegetation. Acidification is decreasing more rapidly in the forest compared to the eroding peatland possibly due to the progressive harvesting of the mature forest reducing the scavenging of acidifying inputs. For the Lower Hafren, long-term average annual precipitation is slightly lower, with lower average altitude, at around 2520mm and evaporation is around double that of the Upper Hafren.

In situ speciation measurements of trace metals in headwater streams.

Concentrations of Al, Fe, Mn, Ni, Cu, Cd, Pb, and Zn were measured using DGT (diffusive gradients in thin-films) devices deployed in situ in 34 headwater streams in Northern England. Mean values of filtered samples analyzed by ICP-MS (inductively coupled plasma mass spectrometry) were used, along with DOC (dissolved organic carbon), pH and major ions, to calculate the distribution of metal species using the speciation code WHAM. DGT-measured concentrations, [Me]DGT, of Zn and Cd were generally similar to concentrations in filtered samples, [Me]filt. For the other metals, [Me]DGT was similar to or lower than [Me]filt. Calculation of the maximum dynamic metal from the speciation predicted using WHAM showed that most of the lower values of [Cu]DGT could be attributed to the dominance of Cu-fulvic acid complexes, which diffuse more slowly than simple inorganic species. Similar calculations for Al, Pb, and Mn were consistent with appreciable proportions of these metals being present as colloids that are not simple complexes with humic substances. Differences between WHAM predictions and the measured [Ni]DGT indicated that WHAM used with the default binding parameters underestimates Ni binding to natural organic matter. Plots of [Me]DGT versus the ratio of bound metal to DOC provided slight evidence of heterogeneous binding of Pb and Cu, while results for Mn, Cd, and Zn were consistent with weak binding and complete lability.