Bioavailability, accumulation and effects of heavy metals in sediments with special reference to United Kingdom estuaries: a review

Using mainly United Kingdom estuaries as examples, various factors governing the bioavailability, bioaccumulation and biological effects of heavy metals in sediment-dominated estuaries are reviewed. Estuaries and metals primarily discussed include the Mersey (Hg, methylmercury; Pb, alkyllead), the Loughor (Cr, Sn), the Severn (Ag, Cd), the Fal (As, Cu, Sn, Zn), Poole Harbour (Cd, Hg, Se, tributyltin) and Southampton Water (tributyltin). Concentrations and bioavailabilities of metals in estuarine sediments depend on many different processes. Examples include (1) mobilisation of metals to the interstitial water and their chemical speciation, (2) transformation (e.g. methylation) of metals including As, Hg, Pb and Sn (3) the control exerted by major sediment components (e.g. oxides of Fe and organics) to which metals are preferentially bound, (4) competition between sediment metals (e.g. Cu and Ag; Zn and Cd) for uptake sites in organisms, and (5) the influence of bioturbation, salinity, redox or pH on these processes. Under field conditions, identification of dominant processes can be achieved by observing the goodness of fit between metal concentrations in ubiquitous deposit-feeding species and levels in various types of sediment extract over a wide spectrum of sediment types. Factors of more local importance are often indicated by the marked deviation of some points from otherwise excellent relationships. For example, points lying above the line relating tissue Sn concentrations in the clam Scrobicularia plana to those in 1 n HCl extracts of sediments were found to reflect the accumulation of tributyltin, a more readily bioavailable form of Sn. In the same species, unexpectedly high tissue-Cu concentrations were characteristic of very anoxic in sediments and tissue And As and Pb concentrations were suppressed in sediments having high concentrations of Fe oxides. Under field conditions, examples of deleterious effects on benthic organisms that can be attributed to specific metallic pollutants are comparatively rare. Effects of tributyltins from antifouling paints on oysters and neogastropods have been documented and their toxicity has undoubtedly led to environmental degradation in many UK estuaries and coastal areas. In estuaries contaminated with metal-mining wastes, the effects of Cu and Zn on species distribution can be observed, but they are generally less obvious than would be predicted from experimental data. Effects are ameliorated by the induction of metal tolerance mechanisms in some species and in others by the appearance of tolerant strains. The induction of metal detoxification systems involving the formation of granules or metal-binding proteins leads in some species to tissue concentrations that are orders of magnitude higher than normal. For example, high concentrations of Cd and Ag have been found in some species from the Severn Estuary, although there is no unequivocal evidence that either metal has caused deleterious effects on benthic populations. On the other hand, experimental studies with Ag, Cd, Cr, Cu, Hg and Zn show that they are toxic to some species at environmentally realistic levels. Since pollutants rarely occur singly, it is likely that in many moderately contaminated estuaries metals contribute to the stress to organisms caused by substances requiring detoxification. There has been much speculation over the years concerning the biomagnification of metals with increasing trophic levels along food chains. Whilst animals having higher metal concentrations than their prey are sometimes found, the only consistent evidence of biomagnification concerns methylmercury. When estuarine birds are considered, there are relatively few instances in which deleterious effects can unequivocally be attributed to metals or their compounds. However, the Mersey bird kill was attributable to alkyllead pollution from industry. Among other organometals, methylmercury has proved toxic to birds but, so far, no evidence for the toxicity of tributyltin has been reported. However, the compound may have affected bird populations through its effects on the abundance of prey organisms, particularly estuarine molluscs. Of the inorganic forms of metals, Pb in the form of shot has caused problems in many areas and Cd, Hg and Se are suspected of causing toxic effects. There is little field evidence that birds have been affected by Ag, As, Cr, Cu or Zn individually. On the other hand, it is difficult to exclude the possibility that, additively, these metals may produce a significant effect. In part, the lack of evidence reflects the fact that relatively little research has been done. There is scope for more work on metals and organometals in estuarine birds, particularly with regard to their metabolism and their effects on juveniles and individuals subjected to stresses such as starvation.     

Contribution of canopy leaching to sulphate deposition in a Scots pine forest

Radioactive sulphate (35SO4) was applied to the soil below a Scots pine forest on 23 June 1989, and its movement into the canopy and into throughfall and stemflow was measured over 4 months. The specific activity, Bq (mg S)(-1), of the canopy increased monotonically; uptake by current-year (1989) expanding needles was initially twice as fast as by older needles or live twigs. By 10 October the canopy average specific activity was 62 Bq (mg S)(-1). The specific activity of net throughfall (throughfall + stemflow - rain), deduced from measurements from six throughfall collectors, six stemflow collectors and two rain collectors, fell rapidly from 12.6 Bq (mg S)(-1) in late July to <1 Bq (mg S)(-1) in mid-August. The results suggest (assuming rapid equilibration of 35S with sulphate in soil) that root-derived sulphate contributed c. 3% of sulphate in net throughfall and that dry deposition of SO2 and sulphate particles contributed c. 97% of the 0.56 g S m(-2) measured in net throughfall over the period. Simultaneous measurements of SO2 at canopy height and of NH3 above and within the canopy gave mean concentrations of 5.9 and 0.86 microg m(-3), respectively, sufficient to account for the sulphate measured in net throughfall only if codeposition of NH3 and SO2 occurred to canopy surfaces. The large values of specific activity observed in July, however, indicate that throughfall composition may be closely related to recent soil input of sulphate, and that equilibrium cannot be safely assumed. The possibility of a significant contribution of soil-derived sulphate to sulphate deposition in net throughfall cannot be ruled out on the basis of this experiment.     

Impact of atrazine-bearing agricultural tile drainage discharge on planktonic drift of a natural stream

Preliminary results are reported from a co-operative study between Agriculture Canada and Environment Canada on environmental impacts of atrazine measured in a field stream receiving agricultural drainage. Systematically, tile drained plots of known crop rotation, area, flow and pesticides use were used in the study. A maximum tile drainage concentration of 13.9 microg liter(-1) atrazine was measured while the maximum measured stream concentration was 1.89 microg liter(-1). Phytoplankton and zooplankton samples were collected on a bi-monthly basis during the growing season. The study indicated possible negative impacts of low concentrations of atrazine on planktonic drift populations, when natural stream flow was reduced, resulting in a lower dilution capacity. A 20 m section of the stream was affected by the tile drainage waters as measured by the resident biological community. Both atrazine and ambient environmental conditions were felt to be contributing to the measured results. No negative impacts on planktonic drift populations were evident beyond 50 m downstream of the tile drainage and stream confluence.     

A review of the likely causal pathways relating the reduced density of breeding dippers Cinclus cinclus to the acidification of upland streams

Previous work has shown that the breeding density of a bird characteristic of upland streams, the dipper Cinclus cinclus, is markedly reduced at low pH in both Wales and Scotland. Populations also declined when streams became more acidic. Evidence of causal explanation for these relationships is that: (1) Food quantity is reduced in acidic streams, and important prey, including those rich in calcium, are scarce; (2) Blood chemistry in pre-breeding birds differs between acid and circumneutral streams, with plasma calcium reduced in those breeding at low pH. Skeletal sources of calcium are probably limited; (3) The time spent foraging by pre-breeding birds on acidic streams is markedly increased, even though overall energy costs on acidic and circumneutral streams are similar. Body condition is inferior to birds on circumneutral streams; (4) Egg laying is significantly delayed on acidic streams irrespective of an effect on laying of altitude, and clutch and brood sizes are significantly reduced; (5) Eggs are lighter and shells thinner at low pH; (6) Chick growth is reduced at low pH; (7) Contamination by heavy metals and persistent organochlorines is low in the populations on acidic streams and cannot explain the impaired breeding performance. None of these features can exclude the possibilities that acidic streams either hold populations of poor quality birds, which show the above features, or that acidity affects the breeding ecology of all dippers that attempt to breed at low pH. The qualitative outcome of these two alternatives is identical.     

Deposition of atmospheric ammonia to moorlands

Micrometeorological methods were applied to measure fluxes of atmospheric ammonia (NH3) to moorlands. Measurements were made in a wide variety of surface conditions and included both Calluna vulgaris (L.) Hull and Eriophorum vaginatum L. dominated sites. NH3 was found to deposit rapidly to all the sites investigated, providing large deposition velocities (Vd, typically 10-40 mm s(-1)) and usually minimal surface resistances (rc). A small number of measurements were made in frozen conditions and suggest a possible exception to this pattern with mean rc of 50-200 s m(-1). The effect of vegetation drying was also investigated and a possible increase in rc observed, though this was small (< 10 s m(-1)). The results are interpreted in terms of the processes controlling exchange; it is shown that NH3 deposition is predominantly to the leaf surfaces and that the net NH3 compensation point approaches zero. Annual estimates show that dry deposition of NH3 is a major source of atmospheric nitrogen to moorland ecosystems. For two typical UK sites subject to background air concentrations, NH3 dry deposition is of similar magnitude to equivalent NH4+ inputs in wet deposition. In the vicinity of emission sources, NH3 dry deposition is expected to dominate inputs of atmospheric nitrogen.     

Modelling episodic acidification of surface waters: the state of science

Field studies of chemical changes in surface waters associated with rainfall and snowmelt events have provided evidence of episodic acidification of lakes and streams in Europe and North America. Modelling these chemical changes is particularly challenging because of the variability associated with hydrological transport and chemical transformation processes in catchments. This paper provides a review of mathematical models that have been applied to the problem of episodic acidification. Several empirical approaches, including regression models, mixing models and time series models, support a strong hydrological interpretation of episodic acidification. Regional application of several models has suggested that acidic episodes (in which the acid neutralizing capacity becomes negative) are relatively common in surface waters in several regions of the US that receive acid deposition. Results from physically based models have suggested a lack of understanding of hydrological flowpaths, hydraulic residence times and biogeochemical reactions, particularly those involving aluminum. The ability to better predict episodic chemical responses of surface waters is thus dependent upon elucidation of these and other physical and chemical processes.     

Towards an assessment of the influence of climate on wet acidic deposition in Europe

The EMEP precipitation composition network is used to examine relationships between non-marine SO4(2-), NO3-, NH4+, H+ concentrations and precipitation amount and a local zonal pressure index (an index of the atmospheric circulation). The pattern of the relationships changes across Europe with the zonal pressure gradient explaining more of the variance in ion concentrations in the west, and precipitation amount explaining relatively more of the variance in the east. There is some predictive capability for precipitation composition in the zonal pressure gradient for restricted regions in Europe; R2 values are up to 40% on a daily basis but in some seasons/months attain >60%. The zonal pressure gradient is an index which appears to include pertinent information on transport and wet removal. Preliminary analysis indicates that this approach can be useful in assessing the contributions of changing atmospheric circulation to time-trends of wet acidic deposition in an area stretching from the UK over the North Sea to Denmark. The zonal pressure gradient is known to have varied on time-scales of decades, and the simple index may be one appropriate approach to assessing future deposition patterns from future climate projections.     

Comparison of episodic acidification in Canada, Europe and the United States

Episodic acidification is practically a ubiquitous process in streams and drainage lakes in Canada, Europe and the United States. Depressions of pH are often smaller in systems with low pre-episode pH levels. Studies on European surface waters have reported episodes most frequently with minimum pH levels below 4.5. In Canada and the United States, studies have also reported a number of systems that have had minimum pH levels below 4.5. In all areas, change in water flowpath during hydrological events is a major determinant of episode characteristics. Episodic acidification is also controlled by a combination of other natural and anthropogenic factors. Base cation decreases are an important contributor to episodes in circumneutral streams and lakes. Sulphate pulses are generally important contributors to episodic acidification in Europe and Canada. Nitrate pulses are generally more important to episodic acidification in the Northeast United States. Increases in organic acids contribute to episodes in some streams in all areas. The sea-salt effect is important in near-coastal streams and lakes. In Canada, Europe and the United States, acidic deposition has increased the severity (minimum pH reached) of episodes in some streams and lakes.     

Effects of clearfelling on stream and soil water aluminium chemistry in three UK forests

Data are presented demonstrating how clearfelling has changed soil and stream water aluminium chemistry. For soil waters, a strong empirical relationship was observed between inorganic aluminium (Al(inorg)) and total inorganic anion (TIA) concentrations. Before felling, chloride and sulphate accounted for the largest proportion of the TIA concentration. After felling, in soils where nitrification was active, nitrate became increasingly important. Where this led to an increase in TIA, Al(inorg) concentrations increased. Over five years, nitrate concentrations have fallen, along with TIA, resulting in a sympathetic decline in Al(inorg). Streams draining clearfelled areas initially became more acid, although chloride and sulphate concentrations decreased. Stream water nitrate concentrations increased soon after felling and remained higher than controls for up to four years. While nitrate concentrations were high, Al(inorg) remained unchanged. Subsequently, as nitrate and TIA decreased, Al(inorg) also declined to concentrations below those in the control stream. Clearfelling upland forests will not necessarily result in immediate improvements in water quality, although long-term benefits may be seen before canopy-closure of the next crop.     

Observations of H2O2 and PAN in a rural atmosphere

Measurements of gaseous H2O2 and peroxyacetyl nitrate (PAN) concentrations in air are given for a site in rural southern England over an approximately 4-year period. In both cases the data show both diurnal and seasonal patterns. Temperature and wind direction had clear influences on the recorded concentrations of both species. There was an indication of increasing H2O2 concentrations with time. The use of a two-dimensional global model confirmed that this would be expected to occur alongside growth in ozone formation. It is suggested that, during photochemical episodes, the sequential build-up of ozone, PAN and H2O2 could be important in influencing the ability of vegetation to resist the effects of aggressive pollutants.