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.     

Ozone in the urban southeastern United States

Ozone measurements (daily maximum values) from the Aerometric Information Retrieval System database are analyzed for selected sites, during 1980 to 1988, in southeastern USA. Frequency distributions, for most sites during most years, show a typical bell-shaped curve with the higher frequency around the yearly daily maximum ozone mean of about 100 to about 110 microg m(-3) (50-55 ppbv). Abnormal years in ozone concentration may skew the distribution as the mean shifts. A correlation of daily maximum ozone concentrations above 140 microg m(-3) (70 ppbv) between sites shows a division between the sites in the northern protion of the region and those in the southern portion of the region. Variations in ozone levels are well correlated over distances of several hundred kilometers, suggesting that high values are associated with synoptic scale episodes. An ozone exposure analysis also shows higher ozone exposures (250-300 ppm days) in the northerly sites as compared to the southerly sites (150-170 ppm days).     

Effect of nickel on some aspects of protein metabolism in the gill and kidney of the freshwater fish, Cyprinus carpio L

Nickel has an adverse effect on some aspects of protein metabolism of the freshwater fish, Cyprinus carpio. The main changes observed were: (a) Decrease in soluble, structural and total proteins, AlAT and AAT activities with an increase in the levels of free amino acids, protease and GDH activities and ammonia in the gill and kidney at 1, 2, 3, and 4 days of exposure to a lethal concentration, 40 mg litre(-1) of nickel; (b) Increase in soluble, structural and total proteins, free amino acids and the activities of protease, AlAT, AAT and GDH with a decrease in ammonia and urea in these organs at 1, 5, 10 and 15 days of exposure to sublethal concentration, 8 mg litre(-1); (c) The magnitude in these changes increased over time with both concentrations of the metal, and was more marked in gill than in kidney.     

The response of stream-dwelling fish to liming

The fish fauna in 22 limed and seven unlimed small streams was monitored using yearly electrofishing to assess the effects of liming on species occurrence and abundance. The liming techniques were divided into three main methods, lake liming, doser liming and wetland liming, to evaluate whether different strategies had different effects on the fish fauna. The predominant species at the investigated stations were salmonids, mainly brown trout (Salmo trutta) and Atlantic salmon (Salmo salar). Other species generally occurred in low numbers. The average number of fish species did not increase significantly after liming, which was probably due to recolonization difficulties caused by the frequent occurrence of migration obstacles in the streams. After liming the density of salmonids increased significantly, irrespective of the liming method. Other fish species showed no general increase, but in individual streams significant increases of European minnow (Phoxinus phoxinus) and bullhead (Cottus gobio) occurred. Some unlimed streams had acid spates with a pH below 6, which immediately lowered the numbers of salmonid parr. Other unlimed streams lost fish species progressively due to increasing acidification. pH, and probably increased levels of metals, were the major factors regulating the fish fauna. Few examples of biotic interactions were observed, but with an increase of Atlantic salmon parr after liming, brown trout abundances decreased in three streams.     

Altered feeding preference of beech weevil Rhynchaenus fagi L. for beech foliage under ambient air pollution

The effect of ambient air pollution with increased ozone concentrations on the feeding behaviour of the beech weevil Rhynchaenus fagi L. was studied. In a dual choice feeding test the beech weevil preferred leaf disks from beech saplings exposed to ambient air against those from filtered air in 65.5% of all cases.     

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.     

Fluxes of ions in precipitation, throughfall and stemflow in an urban forest in Kuala Lumpur, Malaysia

A study was carried out to determine the chemical composition of bulk precipitation, throughfall and stemflow in an urban forest in Kuala Lumpur, Malaysia. The mean weekly rainfall recorded during the period of study was 63.2 mm. Throughfall, stemflow and canopy interception of incident precipitation were 77.1%, 1.2% and 21.7% respectively. Bulk precipitation, througfall and stemflow were acidic, the pH recorded being 4.37, 4.71 and 4.15 respectively. In all cases the dominant ions were NO3, SO4, Cl, NH4, K, Ca and Na. Of the ions studied Ca, K, Cl, SO4, Mg and Mn showed net increases in passing through the forest canopy, while NH4, Na, NO3, Zn, H and Fe showed net retention. This study shows that the urban environment of Kuala Lumpur contributes considerable amounts of materials to the atmosphere, as reflected by the high ionic contents in bulk precipitation, throughfall and stemflow.     

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.     

Factors affecting trace-metal bioaccumulation in Finnish headwater lakes

Fourteen unpolluted Finnish headwater lakes with pH values varying from 4.8 to 7.0 were studied for trace-metal concentrations in water, sediment, aquatic plants (Nuphar luteum L., Sparganium sp.), aquatic insect larvae (Limnophilus sp., Phryganea sp.) and fish (Esox lucius L., Perca fluviatilis L., Coregonus sp., Salvelinus fontinalis L., Salmo trutta L.). Trace-metal deposition was estimated by analysing the snowpack. Non-parametric correlation analysis was carried out between trace metal concentrations in biota and pH, ANC, TOC, CA + Mg concentration in water and a given metal concentration in water and sediment. Bioaccumulation of several trace metals increased with increasing acidity and decreasing ANC in water. This was especially true for Pb and Cd. Aquatic plants were, in general, the best indicator group concerning differences in trace-metal bioaccumulation in lakes with different acidity. There was some evidence that a higher concentration of TOC in water may reduce bioaccumulation of Pb, Cd and Zn in aquatic plants and fish. The copper concentration in sediment was the only background variable explaining Cu concentration in aquatic insects. Multivariate analysis of the whole background data gave comparable preliminary results. Over 80% of the trace metal concentrations in biota of different lakes was explained by the background variables. In general, elevated concentrations of most of these trace metals can be expected to occur in the biota of acidified low calcareous lakes.     

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.