Manganese concentrations in Scottish groundwater

Groundwater is increasingly being used for public and private water supplies in Scotland, but there is growing evidence that manganese (Mn) concentrations in many groundwater supplies exceed the national drinking water limit of 0.05 mg l^− 1. This study examines the extent and magnitude of high Mn concentrations in groundwater in Scotland and investigates the factors controlling Mn concentrations. A dataset containing 475 high quality groundwater samples was compiled using new data from Baseline Scotland supplemented with additional high quality data where available. Concentrations ranged up to 1.9 mg l^− 1; median Mn concentration was 0.013 mg l^− 1 with 25th and 75th percentiles 0.0014 and 0.072 mg l^− 1 respectively. The Scottish drinking water limit (0.05 mg l^− 1) was exceeded for 30% of samples and the WHO health guideline (0.4 mg l^− 1) by 9%; concentrations were highest in the Carboniferous sedimentary aquifer in central Scotland, the Devonian sedimentary aquifer of Morayshire, and superficial aquifers. Further analysis using 137 samples from the Devonian aquifers indicated strong redox and pH controls (pH, Eh and dissolved oxygen accounted for 58% of variance in Mn concentrations). In addition, an independent relationship between Fe and Mn was observed, suggesting that Fe behaviour in groundwater may affect Mn solubility. Given the redox status and pH of Scottish groundwaters the most likely explanation is sorption of Mn to Fe oxides, which are released into solution when Fe is reduced.Since the occurrence of elevated Mn concentrations is widespread in groundwaters from all aquifer types, consideration should be given to monitoring Mn more widely in both public and private groundwater supplies in Scotland and by implication elsewhere.     

Solving the problem at the source: Controlling Mn release at the sediment-water interface via hypolimnetic oxygenation

One of the primary goals of hypolimnetic oxygenation systems (HOx) from a drinking water perspective is to suppress sediment-water fluxes of reduced chemical species (e.g., manganese and iron) by replenishing dissolved oxygen (O₂) in the hypolimnion. Manganese (Mn) in particular is becoming a serious problem for water treatment on a global scale. While it has been established that HOx can increase sediment O₂ uptake rates and subsequently enhance the sediment oxic zone via elevated near-sediment O₂ and mixing, the influence of HOx on sediment-water fluxes of chemical species with more complicated redox kinetics like Mn has not been comprehensively evaluated.This study was based on Mn and O₂ data collected primarily in-situ to characterize both the sediment and water column in a drinking-water-supply reservoir equipped with an HOx. While diffusive Mn flux out of the sediment was enhanced by HOx operation due to an increased concentration driving force across the sediment-water interface, oxygenation maintained elevated near-sediment and porewater O₂ levels that facilitated biogeochemical cycling and subsequent retention of released Mn within the benthic region. Results show that soluble Mn levels in the lower hypolimnion increased substantially when the HOx was turned off for as little as ∼48 h and the upper sediment became anoxic. Turning off the HOx for longer periods (i.e., several weeks) significantly impaired water quality due to sediment Mn release. Continual oxygenation maintained an oxic benthic region sufficient to prevent Mn release to the overlying source water.     

A comparative analysis of iron,manganese, silica,phosphorus, and sulfur in the hypolimnia of calcareous lakes

The chemistry of the hypolimnion was studied in late summer in 23 individual basins of 19 calcareous lakes situated in the Midwestern U.S.A. The basins represented a broad range in morphometry, and drainage basin influences. All but two of the basins were anoxic by early September.The concentrations of Fe were low in the anoxic basins because of precipitation of FeS. Excess sulfide accumulated in the hypolimnion (up to 7 mg 1⁻¹) making these basins sulfuretums. The concentrations of total-P ranged widely—from 0.03 mg 1⁻¹ in several seepage lakes to > 0.5 mg 1⁻¹ in drainage lakes with very short τ_w, or influenced by agricultural or urban drainage, or municipal waste. Neither apatite nor vivianite limited the hypolimnetic build-up of this key nutrient. Hypolimnetic Mn was almost entirely soluble if the basin was anoxic. The concentrations indirectly reflected external inputs, not the thermodynamics of rhodochrosite. Concentrations of dissolved silica were generally much lower than in inflowing waters. The hypolimnetic Si/P ratio was low unless the lake lacked surface inflows and also experienced high rates of groundwater inflow rich in silica and very low in P.Because of the very low hypolimnetic Fe/P and Fe/Si ratios, phosphate and silica are liberated from significant chemical interactions with Fe accompanying their eddy diffusion transport upward within the hypolimnion, and across the metalimnetic oxycline. Because of external P inputs and the efficiency of internal P recycling, Si is potentially a limiting nutrient for diatoms in calcareous lakes.     

Risk of acute toxicity for fish during aluminium application to hardwater lakes

To assess the risk of aluminium (Al) toxicity during the restoration of the eutrophic lake Tiefwarensee by hypolimnetic addition of NaAl(OH)₄-solution (aluminate) the generally limnological monitoring was accompanied by fractionation of Al in water and using Al accumulation on fish gills as bioindicator. The concentration of reactive Al species in the alkaline water (pH 8) peaked at 2 mg L^− 1 in parts of the anoxic hypolimnion and was 0.088 ± 0.053 mg L^− 1 (n = 70) in the epilimnion during the five years of treatment. During an Al treatment cycle in summer 2003, perches showed significant Al accumulation on gills (100 µg Al g^− 1 dw) whereas roaches, breams and silver carps remained unaffected. Thus, the Al toxicity towards several fish species seems to be low, although the concentration of reactive Al in the lake water increased by a factor of 2. However, high Al toxicity due to lake treatment with aluminate could not be excluded, as high Al-gill concentration was observed. An Al balance two years after the treatment indicates complete export of the added Al into the sediment.     

Temporal variations in arsenic uptake by rice plants in Bangladesh: The role of iron plaque in paddy fields irrigated with groundwater

The transfer of arsenic to rice grains is a human health issue of growing relevance in regions of southern Asia where shallow groundwater used for irrigation of paddy fields is elevated in As. In the present study, As and Fe concentrations in soil water and in the roots of rice plants, primarily the Fe plaque surrounding the roots, were monitored during the 4-month growing season at two sites irrigated with groundwater containing ∼ 130 μg l^− 1 As and two control sites irrigated with water containing < 15 μg l^− 1 As. At both sites irrigated with contaminated water, As concentrations in soil water increased from < 10 μg l^− 1 to > 1000 μg l^− 1 during the first five weeks of the growth season and then gradually declined to < 10 μg l^− 1 during the last five weeks. At the two control sites, concentrations of As in soil water never exceeded 40 µg l^− 1. At both contaminated sites, the As content of roots and Fe plaque rose to 1000-1500 mg kg^− 1 towards the middle of the growth season. It then declined to ∼ 300 mg kg^− 1 towards the end, a level still well above As concentration of ∼ 100 mg kg^− 1 in roots and plaque measured throughout the growing season at the two control sites. These time series, combined with simple mass balance considerations, demonstrate that the formation of Fe plaque on the roots of rice plants by micro-aeration significantly limits the uptake of As by rice plants grown in paddy fields. Large variations in the As and Fe content of plant stems at two of the sites irrigated with contaminated water and one of the control sites were also recorded. The origin of these variations, particularly during the last month of the growth season, needs to be better understood because they are likely to influence the uptake of As in rice grains.     

Heavy metals: confounding factors in the response of New Zealand freshwater fish assemblages to natural and anthropogenic acidity

Acidification of freshwaters is a global phenomenon, occurring both through natural leaching of organic acids and through human activities from industrial emissions and mining. The West Coast of the South Island, New Zealand, has both naturally acidic and acid mine drainage (AMD) streams enabling us to investigate the response of fish communities to a gradient of acidity in the presence and absence of additional stressors such as elevated concentrations of heavy metals. We surveyed a total of 42 streams ranging from highly acidic (pH 3.1) and high in heavy metals (10 mg L⁻¹ Fe; 38 mg L⁻¹ Al) to circum-neutral (pH 8.1) and low in metals (0.02 mg L⁻¹ Fe; 0.05 mg L⁻¹ Al). Marked differences in pH and metal tolerances were observed among the 15 species that we recorded. Five Galaxias species, Anguilla dieffenbachii and Anguillaaustralis were found in more acidic waters (pH< 5), while bluegill bullies (Gobiomorphus hubbsi) and torrentfish (Cheimarrichthys fosteri) were least tolerant of low pH (minimum pH 6.2 and 5.5, respectively). Surprisingly, the strongest physicochemical predictor of fish diversity, density and biomass was dissolved metal concentrations (Fe, Al, Zn, Mn and Ni) rather than pH. No fish were detected in streams with dissolved metal concentrations > 2.7 mg L⁻¹ and nine taxa were only found in streams with metal concentrations < 1 mg L⁻¹. The importance of heavy metals as critical drivers of fish communities has not been previously reported in New Zealand, although the mechanism of the metal effects warrants further study. Our findings indicate that any remediation of AMD streams which seeks to enable fish recolonisation should aim to improve water quality by raising pH above ≈ 4.5 and reducing concentrations of dissolved Al and Fe to < 1.0 mg L⁻¹.     

Performance of a passive treatment system for net-acidic coal mine drainage over five years of operation

A full-scale passive treatment system (PTS) was commissioned in 2003 to treat two net-acidic coal mine water discharges in the Durham coalfield, UK. The principal aim of the PTS was to decrease concentrations of iron (< 177 mg L⁻¹) and aluminium (< 85 mg L⁻¹) and to increase pH (> 3.2) and alkalinity (≥ 0 mg L⁻¹ CaCO₃ eq). Secondary objectives were to decrease zinc (< 2.8 mg L⁻¹), manganese (< 20.5 mg L⁻¹) and sulfate (< 2120 mg L⁻¹). Upon treatment, water qualities were improved by 84% in the case of Fe, 87% Al, 83% acidity, 51% Zn, 23% Mn and 29% SO₄²⁻. Alkalinity (74%) and pH (95% as H⁺) were increased. Area adjusted removal rates (Fe = 1.49 ± 0.66 g d⁻¹ m⁻²; acidity = 6.7 ± 4.9 g d⁻¹ m⁻²) were low compared to design criteria, mainly due to load limitation. Disregarding seasonality effects, acidity removal and effluent pH were stable over time. A substantial temporal decrease in calcium and alkalinity generation suggests that limestone is increasingly armoured. Once pH is no longer buffered by the carbonate system, metals could be remobilized, putting treatment efficiency at risk.     

Nitrogen and phosphorus removal from an abattoir wastewater in a SBR with aerobic granular sludge

The formation and performance of granular sludge was studied in an 8 l sequencing batch reactor (SBR) treating an abattoir (slaughterhouse) wastewater. Influent concentrations averaged 1520 mg l⁻¹ volatile suspended solids (VSS), 7685 mg l⁻¹ Chemical oxygen demand (COD), 1057 mg l⁻¹ total kjeldahl nitrogen (TKN), 217 mg l⁻¹ total P. The COD loading was 2.6 kg m⁻³ d⁻¹. The SBR was seeded with flocculating sludge from a SBR with an 1 h settle time, but granules developed within 4 days by reducing the settle time to 2 min. The SBR cycle also had 120 min mixed (anaerobic) fill, 220 min aerated react, and 18 min draw/idle. The granules had a mean diameter of 1.7 mm, a specific gravity of 1.035, a density of 62 g VSS l⁻¹, a zone settling velocity (ZSV) of 51 m h⁻¹, and a sludge volume index (SVI) of 22 ml g⁻¹. Without optimizing process conditions, removal of COD and P were over 98%, and removal of N and VSS were over 97%. Nitrification and denitrification occurred simultaneously during react. The results indicate that conventional SBRs treating wastewaters with flocculating sludge can be converted to granular SBRs by reducing the settle time.     

Changes in water quality of the River Frome (UK) from 1965 to 2009: is phosphorus mitigation finally working?

The water quality of the River Frome, Dorset, southern England, was monitored at weekly intervals from 1965 until 2009. Determinands included phosphorus, nitrogen, silicon, potassium, calcium, sodium, magnesium, pH, alkalinity and temperature. Nitrate-N concentrations increased from an annual average of 2.4 mg l^− 1 in the mid to late 1960s to 6.0 mg l^− 1 in 2008-2009, but the rate of increase was beginning to slow. Annual soluble reactive phosphorus (SRP) concentrations increased from 101 μg l^− 1 in the mid 1960s to a maximum of 190 μg l^− 1 in 1989. In 2002, there was a step reduction in SRP concentration (average = 88 μg l^− 1 in 2002-2005), with further improvement in 2007-2009 (average = 49 μg l^− 1), due to the introduction of phosphorus stripping at sewage treatment works. Phosphorus and nitrate concentrations showed clear annual cycles, related to the timing of inputs from the catchment, and within-stream bioaccumulation and release. Annual depressions in silicon concentration each spring (due to diatom proliferation) reached a maximum between 1980 and 1991, (the period of maximum SRP concentration) indicating that algal biomass had increased within the river. The timing of these silicon depressions was closely related to temperature. Excess carbon dioxide partial pressures (EpCO₂) of 60 times atmospheric CO₂ were also observed through the winter periods from 1980 to 1992, when phosphorus concentration was greatest, indicating very high respiration rates due to microbial decomposition of this enhanced biomass. Declining phosphorus concentrations since 2002 reduced productivity and algal biomass in the summer, and EpCO₂ through the winter, indicating that sewage treatment improvements had improved riverine ecology. Algal blooms were limited by phosphorus, rather than silicon concentration. The value of long-term water quality data sets is discussed. The data from this monitoring programme are made freely available to the wider science community through the CEH data portal (http://gateway.ceh.ac.uk/).     

Ecotoxicological assessment of a polyelectrolyte flocculant

Flocculant blocks are commonly used as a component of (passive) water treatment systems to reduce suspended sediment loads in the water column. This study investigated the potential for aquatic biological impacts of a flocculant block formulation that contained an anionic polyacrylamide (PAM) active ingredient and a polyethylene glycol (PEG) based carrier. The toxicity of the whole flocculant block was assessed and the individual components of the block were also tested separately. Five Northern Australian tropical freshwater species (i.e. Chlorella sp. Lemna aequinoctialis, Hydra viridissima, Moinodaphnia macleayi and Mogurnda mogurnda) were exposed to a range of concentrations of the whole flocculant block, and of the individual PAM and PEG components. The concentration of Total Organic Carbon (TOC) in solution was used to provide a measure of the total amount of PAM and PEG present. An extremely wide range of toxic responses were found, with the flocculant blocks being essentially non-toxic to the duckweed, fish and algae (IC₅₀ > 1880 mg l⁻¹ C TOC, IC₁₀ > 460 mg l⁻¹ C TOC), slightly toxic to the hydra (IC₅₀ = 610-2180 mg l⁻¹ C TOC, IC₁₀ = 80-60 mg l⁻¹ C TOC) and significantly more toxic to the cladoceran (IC₅₀ = 10 mg l⁻¹ C TOC, IC₁₀ = 4 mg l⁻¹ C TOC). More detailed investigation of the two components indicated that the PAM was the primary “toxicant” in the flocculant blocks. Derived Protective Concentrations (PCs) for the flocculant blocks, expressed as equivalent TOC concentrations, were found to be lower than typically measured natural environmental concentrations of TOC. It will thus be possible to use TOC as measure of the concentration of PAM only in those situations where lower levels of ecosystem protection (i.e. higher PCs) are applicable.     

Occurrence of arsenic in core sediments and groundwater in the Chapai-Nawabganj District, northwestern Bangladesh

Groundwater and core sediments of two boreholes (to a depth of 50 m) from the Chapai-Nawabganj area in northwestern Bangladesh were collected for arsenic concentration and geochemical analysis. Groundwater arsenic concentrations in the uppermost aquifer (10-40 m of depth) range from 2.8 μg L⁻¹ to 462.3 μg L⁻¹. Groundwater geochemical conditions change from oxidized to successively more reduced, higher As concentration with depth. Higher sediment arsenic levels (55 mg kg⁻¹) were found within the upper 40 m of the drilled core samples. X-ray absorption near-edge structure spectroscopy was employed to elucidate the arsenic speciation of sediments collected from two boreholes. Environmental scanning electron microscopy and transmission X-ray microscopy were used to investigate the characteristics of FeOOH in sediments which adsorb arsenic. In addition, a pH-Eh diagram was drawn using the Geochemist's Workbench (GWB) software to elucidate the arsenic speciation in groundwater. The dominant groundwater type is Ca-HCO₃ with high concentrations of As, Fe and Mn but low levels of NO₃⁻ and SO₄²⁻. Sequential extraction analysis reveals that Mn and Fe hydroxides and organic matter are the major leachable solids carrying As. High levels of arsenic concentration in aquifers are associated with fine-grained sediments. Fluorescent intensities of humic substances indicate that both groundwater and sediments in this arsenic hotspot area contain less organic matter compared to other parts of Bengal basin. Statistical analysis clearly shows that As is closely associated with Fe and Mn in sediments while As is better correlated with Mn in groundwater. These correlations along with results of sequential leaching experiments suggest that reductive dissolution of MnOOH and FeOOH mediated by anaerobic bacteria represents an important mechanism for releasing arsenic into the groundwater.     

Environmental impact of mining activities in the Lousal area (Portugal): chemical and diatom characterization of metal-contaminated stream sediments and surface water of Corona stream

Lousal mine is a typical “abandoned mine” with all sorts of problems as consequence of the cessation of the mining activity and lack of infrastructure maintenance. The mine is closed at present, but the heavy metal enriched tailings remain at the surface in oxidizing conditions. Surface water and stream sediments revealed much higher concentrations than the local geochemical background values, which the “Contaminated Sediment Standing Team” classifies as very toxic. High concentrations of Cu, Pb, Zn, As, Cd and Hg occurred within the stream sediments downstream of the tailings sites (up to: 817 mg kg⁻¹ As, 6.7 mg kg⁻¹ Cd, 1568 mg kg⁻¹ Cu, 1059 mg kg⁻¹ Pb, 82.4 mg kg⁻¹ Sb, 4373 mg kg⁻¹ Zn). The AMD waters showed values of pH ranging from 1.9 to 2.9 and concentrations of 9249 to 20,700 mg L⁻¹ SO₄⁻², 959 to 4830 mg L⁻¹ Fe and 136 to 624 mg L⁻¹ Al. Meanwhile, the acid effluents and mixed stream waters also carried high contents of SO₄^2−, Fe, Al, Cu, Pb, Zn, Cd, and As, generally exceeding the Fresh Water Aquatic Life Acute Criteria. Negative impacts in the diatom communities growing at different sites along a strong metal pollution gradient were shown through Canonical Correspondence Analysis: in the sites influenced by Acid Mine Drainage (AMD), the dominant taxon was Achnanthidium minutissimum. However, Pinnularia acoricola was the dominant species when the environmental conditions were extremely adverse: very low pH and high metal concentrations (sites 2 and 3). Teratological forms of Achnanthidium minutissimum (Kützing) Czarnecki, Brachysira vitrea (Grunow) Ross in Hartley, Fragilaria rumpens (Kützing) G. W. F. Carlson and Nitzschia hantzschiana Rabenhorst were found. A morphometric study of B. vitrea showed that a decrease in size was evident at the most contaminated sites. These results are evidence of metal and acidic pollution.     

Effect of COD/SO(4)(2-) ratio and sulfide on thermophilic (55 degrees C) sulfate reduction during the acidification of sucrose at pH 6

This study investigated the effect of the COD/SO₄²⁻ ratio (4 and 1) and the sulfide concentration on the performance of thermophilic (55 °C) acidifying (pH 6) upflow anaerobic sludge bed reactors fed with sucrose at an organic loading rate of 4.5 g COD l_reactor⁻¹ day⁻¹. Sulfate reduction efficiencies amounted to 65% and 25-35% for the COD/SO₄²⁻ ratios of 4 and 1, respectively. Acidification was complete at all the tested conditions and the electron flow was similar at the two COD/SO₄²⁻ ratios applied. The stepwise decrease of the sulfide concentrations in the reactors with a COD/SO₄²⁻ ratio of 1 by N₂ stripping caused an immediate stepwise increase in the sulfate reduction efficiencies, indicating a reversible inhibition by sulfide. The degree of reversibility was, however, affected by the growth conditions of the sludge. Acidifying sludge pre-grown at pH 6, at a COD/SO₄²⁻ ratio of 9 and exposed for 150 days to 115 mg l⁻¹ sulfide, showed a slower recovery from the sulfide inhibition than a freshly harvested sludge from a full scale treatment plant (pH 7 and COD/SO₄²⁻=9.5) exposed for a 70 days to 200 mg l⁻¹ sulfide. In the latter case, the decrease of the sulfide concentration from 200 to 45 mg l⁻¹ (35 mg l⁻¹ undissociated sulfide) by N₂ stripping caused an immediate increase of the sulfate reduction efficiency from 35% to 96%.     

Manganese flux associated with dissolved and suspended manganese forms in Lake Fukami-ike

Redissolved, particulate and sedimentary managanese were studied in the anoxic hypolimnion of the small monomictic Lake Fukami-ike in central Japan. The amounts of particulate and dissolved manganese in the water column were observed. The release of dissolved managanese starts gradually beginning in March. DMn reaches especially high levels of 93 mgMn m⁻² d⁻¹ from the end of May to the end of June calculated from the gradient of a regression formula for the daily change in DMn. The rate of accumulated PMn is 0.64 mgMn m⁻² d⁻¹ from the end of July calculated from the gradient of a regression formula for the daily change in PMn.An accumulation of PMn and an associated decrease in dissolved organic carbon (DOC) were observed at the transition zone of oxic and anoxic layers. These facts seem to suggest that the DOC decrease involves the consumption of DOC as an electron donor by bacterial catalysis for the reduction of MnO₂. The upward and downward DOC fluxes, 0.320 mmolC m⁻² d⁻¹, were calculated by the mean gradient values of the upward and downward DOC concentrations. The mean DOC flux was calculated by both the mean gradient DOC and the vertical diffusion coefficient (0.0304 m⁻² d⁻¹). Manganese-reducing bacteria could contribute as much as 24% to the DOC decrease in the oxic and anoxic layers, considering bacterial assimilation efficiency (64%). Vertical diffusion Mn flux from the interstitial water to the hypolimnion is then assumed to be 2 mgMn m⁻² d⁻¹.Mn for the vertical eddy diffusion flux, the vertical diffusion flux from interstitial water of the bottom sediment, the sinking flux and microbiological Mn flux were obtained, and the biogeochemical managanese cycle in Lake Fukami-ike was calculated. DMn flux in the oxic and anoxic layers by manganese-reducing bacteria is 0.004 gMn m⁻² d⁻¹, a value corresponding to 10% of DMn flux.     

Effect of hypolimnetic oxygenation on oxygen depletion rates in two water-supply reservoirs

Oxygenation systems, such as bubble-plume diffusers, are used to improve water quality by replenishing dissolved oxygen (DO) in the hypolimnia of water-supply reservoirs. The diffusers induce circulation and mixing, which helps distribute DO throughout the hypolimnion. Mixing, however, has also been observed to increase hypolimnetic oxygen demand (HOD) during system operation, thus accelerating oxygen depletion. Two water-supply reservoirs (Spring Hollow Reservoir (SHR) and Carvins Cove Reservoir (CCR)) that employ linear bubble-plume diffusers were studied to quantify diffuser effects on HOD. A recently validated plume model was used to predict oxygen addition rates. The results were used together with observed oxygen accumulation rates to evaluate HOD over a wide range of applied gas flow rates. Plume-induced mixing correlated well with applied gas flow rate and was observed to increase HOD. Linear relationships between applied gas flow rate and HOD were found for both SHR and CCR. HOD was also observed to be independent of bulk hypolimnion oxygen concentration, indicating that HOD is controlled by induced mixing. Despite transient increases in HOD, oxygenation caused an overall decrease in background HOD, as well as a decrease in induced HOD during diffuser operation, over several years. This suggests that the residual or background oxygen demand decreases from one year to the next. Despite diffuser-induced increases in HOD, hypolimnetic oxygenation remains a viable method for replenishing DO in thermally-stratified water-supply reservoirs such as SHR and CCR.     

Spatial and temporal trends in nitrate concentrations in the River Derwent, North Yorkshire, and its need for NVZ status

Long-term spatial and temporal variations in nitrate-N concentrations along the River Derwent have been examined using Environment Agency data to investigate the relative importance of impacts of atmospheric N deposition, land use, and changes in management. Where moorland and rough grazing dominate upstream of Forge Valley and Malton, over the 20 years since 1988 mean nitrate-N concentrations were initially increasing significantly, but are now levelling off, with peaks at ca. 4.5 mg N l⁻¹. As expected in a catchment in a nitrate vulnerable zone (NVZ), more agricultural land use increases mean nitrate concentrations and the occurrence of distinct winter maxima, though the latter have become markedly less pronounced since 2001. It is suggested that this improvement is a combined effect of imposition of NVZ designation in the lower reaches in 2002, animal number declines associated with the Foot & Mouth outbreak in the region in 2001, and the impact of farmers' responses to increasing fertilizer prices and to beneficial pollutant mineral N inputs from the atmosphere. Minima in nitrate-N concentrations in summer have become much less pronounced over the past decade and are typically ca. 60% higher in concentration than a decade earlier. This probably is attributable to the effects of pollutant-N leaching to depths in soil below the rooting zone when near surface biotic uptake is low in winter. The resultant N mineralization in summer enhances summer nitrate leaching. The Derwent is a relatively clean river; however, its entire catchment was designated justifiably as a NVZ in January 2009, apparently based upon a projected 95 percentile nitrate-N concentration > 11.29 mg l^− 1 for 2010 based upon forward projection of data from 1990 to 2004 for Derwent Bridge. A survey of water quality in March 2009 showed that some agricultural areas are still making a significant contribution to the total nitrate level well downstream, at the point responsible for implementation of NVZ status. At 3 of the 29 sites sampled, nitrate concentration exceeded 60 mg l^− 1.     

Significance and interspecific variability of accumulated trace metal concentrations in Antarctic benthic polychaetes

Trace metals were analysed in polychaetes collected on Polarstern cruise ANT XXI/2 (2003/04) to the Weddell Sea. Pb concentrations were largely less than 1.3 mg kg⁻¹ DW in all samples analysed. Statistical results indicate that the accumulated Cd, Cu and Zn concentrations are related to the feeding guild to which the animals are belonging. Relatively low Cd and Cu concentrations are found in macrophagous carnivores and relatively high concentrations in microphagous detritus feeders. The relationship between Zn concentrations and the feeding guilds of polychaetes is reverse. Cd concentrations range from (median values and interquantile ranges in brackets) 2.6 (1.5-3.2) mg kg⁻¹ DW in the carnivorous Trypanosyllis gigantea to 133 (37-176) mg kg⁻¹ in the microphagous detritus feeder Lanicides bilobata; Cu concentrations from 16 (11-19) mg kg⁻¹ in the carnivorous Antarctinoe spicoides to 40 (23-68) mg kg⁻¹ in the microphagous detritus feeder Phyllocomus crocea and Zn from 89 (69-97) mg kg⁻¹ in the microphagous detritus feeder Isocirrus yungi to 396 (372-404) mg kg⁻¹ in the carnivorous Aglaophamus trissophyllus. Ni is ranging from 3.7 (1.8-6.0) mg kg⁻¹ in Polyeunoa laevis to 34 (20-41) mg kg⁻¹ in A. spicoides, but no significant differences are obvious regarding the feeding guilds. Since information on metals in Antarctic polychaetes is almost completely lacking, our results suggest further studies to clarify the role of feeding in the bioaccumulation of metals in this ecologically important taxonomic group.     

Manganese and lead in children's blood and airborne particulate matter in Durban, South Africa

Despite the toxicity and widespread use of manganese (Mn) and lead (Pb) as additives to motor fuels and for other purposes, information regarding human exposure in Africa is very limited. This study investigates the environmental exposures of Mn and Pb in Durban, South Africa, a region that has utilized both metals in gasoline. Airborne metals were sampled as PM_2.5 and PM₁₀ at three sites, and blood samples were obtained from a population-based sample of 408 school children attending seven schools. In PM_2.5, Mn and Pb concentrations averaged 17 ± 27 ng m^− 3 and 77 ± 91 ng m^− 3, respectively; Mn concentrations in PM₁₀ were higher (49 ± 44 ng m^− 3). In blood, Mn concentrations averaged 10.1 ± 3.4 μg L^− 1 and 8% of children exceeded 15 μg L^− 1, the normal range. Mn concentrations fit a lognormal distribution. Heavier and Indian children had elevated levels. Pb in blood averaged 5.3 ± 2.1 μg dL^− 1, and 3.4% of children exceeded 10 μg dL^− 1, the guideline level. Pb levels were best fit by a mixed (extreme value) distribution, and boys and children living in industrialized areas of Durban had elevated levels. Although airborne Mn and Pb concentrations were correlated, blood levels were not. A trend analysis shows dramatic decreases of Pb levels in air and children's blood in South Africa, although a sizable fraction of children still exceeds guideline levels. The study's findings suggest that while vehicle exhaust may contribute to exposures of both metals, other sources currently dominate Pb exposures.     

Influence of soil properties on trace element availability and plant accumulation in a Mediterranean salt marsh polluted by mining wastes: implications for phytomanagement

The aims of this study were to determine the factors which control metal and As phytoavailability in the different microenvironments (Sand Dunes, Salt Flat, Dry River and Shrubs) present at a Mediterranean salt marsh polluted by mining wastes. We performed a field study following a plot sampling survey. The analyses of soil parameters (pH, electrical conductivity (EC), organic carbon contents, etc.), total metal and As concentrations and their phytoavailability assessed with EDTA were related to each microenvironment and the corresponding plant species uptake. The averages of pH and EC were slightly alkaline (pH ≈ 7.5) and saline (≈ 2.2 to 17.1 dS m⁻¹) respectively. The soil samples from the Salt Flat subzone showed the highest metal concentrations (e.g. 51 mg kg⁻¹ Cd, 11,600 mg kg⁻¹ Pb) while for As, the highest concentrations occurred in the Dry River (380 mg kg⁻¹ As). The total metal and EDTA-extractable concentrations occurred as it follows: Salt Flat > Dry River > Degraded Dunes > Shrubs. In relation to plant metal and As accumulation, the highest root concentrations were obtained in the species from the Salt Flat subzone: ~ 17 mg kg⁻¹ As, ~ 620 mg kg⁻¹ Pb, for both, Juncus maritimus and Arthrocnemum macrostachyum. However the highest metal and As shoot concentrations occurred in species from the Sand Dunes: ~ 23 mg kg⁻¹ As ~ 270 mg kg⁻¹ Pb for Dittrichia viscosa; ~ 23 mg kg⁻¹ As, ~ 390 mg kg⁻¹ Zn for Crucianella maritima. The occurrence of edaphic gradients including salinity and texture determined the vegetation distribution. However, it cannot be concluded that there was a disturbance due to metal(loid)s soil concentrations in terms of vegetation composition except in the Degraded Dunes and Dry River. The higher EDTA-extractable concentrations were coincidental with the most saline soils but this did not result in higher metal(loid)s plant accumulation.     

The intake of lead and associated metals by sheep grazing mining-contaminated floodplain pastures in mid-Wales, UK: II. Metal concentrations in blood and wool

Sheep grazing metal-contaminated floodplain pastures across mid-Wales ingest high concentrations of lead (Pb) in vegetation and directly in the form of soil. Sheep whole blood analysis indicated that Pb concentrations can be significantly elevated for animals grazing contaminated sites: in winter/spring, a median blood concentration of 147 µg Pb l^− 1 was found at the location with the highest soil enrichment of this metal compared to only 26 µg Pb l^− 1 for the control flock. There was within-flock variability in blood-Pb concentration, and overlap between blood-Pb ranges in animals grazing control and contaminated sites, although use of the Kruskal-Wallis H test established a number of significant (P < 0.05) differences between the blood-Pb content of flocks grazing the various study locations. Despite total daily intakes of up to 723 mg Pb d^− 1, only one individual sheep showed a blood-Pb content above the ‘normal safe’ concentration of 250 µg l^− 1. Blood and wool analyses were found to have limited value for the diagnosis of environmental exposure to Pb, and further consideration of metal accumulation in offal, bone and muscle tissue is recommended.