Earthworms as biological monitors of cadmium, copper, lead and zinc in metalliferous soils

Earthworms (Lumbricus rebellus and Dendrodrilus rubidus) were sampled from one uncontaminated and fifteen metal-contaminated sites. Significant positive correlations were found between the earthworm and 'total' (conc. nitric acid-extractable) soil Cd, Cu, Pb and Zn concentrations (data log1) transformed). The relationships were linear, and the accumulation patterns for both species were similar when a single metal was considered, even though there were species difference in mean metal concentrations. Generally, the earthworm Cd concentration exceeded that of the soil; by contrast, the worm Pb concentration was lower than the soil Pb concentration in all but one (acidic, low soil Ca) site. Our observations suggest that Cu and Zn accumulation may be physiologically regulated by both species. Total-soil Cd explained 82-86% of the variability (V2) in earthworm Cd concentration; 52-58% of worm Pb and worm Zn concentrations were explained by the total-soil concentrations of the respective metals. Total-soil Cu explained only 11-32% of the worm Cu concentration. The effect of soil pH, total Ca concentration, cation-exchange capacity (CEC) and organic carbon on metal accumulation by L. rubellus and D. rubidus was investigated by multiple regression analysis. Soil pH (coupled with CEC) and soil Ca had a major influence on Pb accumulation (V2 of worm Pb increased to 77-83%), and there was some evidence that Cd accumulation may be suppressed in extremely organic soils. The edaphic factors investigated had no effect on Cu or Zn accumulation by earthworms. In the context of biomonitoring, it is proposed that earthworms have a potential in a dual role: (1) as 'quantitative' monitors of total-soil metal concentrations (as shown for Cd); and (2) as estimators of 'ecologically significant' soil metal, integrating the effects of edaphic factors (as shown for Pb).     

A survey of mercury,lead and cadmium in muscle of British freshwater fish

Analyses of mercury, lead and cadmium in muscle of 221 fish, mainly eel and roach, from 67 sites in Great Britain are presented. Concentrations of metals in a significant number of fish were above recommended standards for human consumption.     

The chronic toxicity of aluminium, cadmium, mercury, and lead in birds: a review

The toxicity of chronic dietary metal exposure in birds is reviewed. It is concluded that significant physiological and biochemical responses to such exposure conditions occur at dietary metal concentrations insufficient to cause signs of overt toxicity. Particularly important are reproductive effects which include decreased egg production, decreased hatchability, and increased hatchling mortality. Young, growing birds are typically more sensitive to the toxic effects of chronic metal exposure than adults, and altricial species are often more sensitive than precocial species. Factors which modify the absorption and toxicity of heavy metals, such as Se for the case of Hg, and Ca for the case of Pb and Cd, are discussed. Monitoring strategies for assessing environmental metal exposure in birds are evaluated.     

Zoobenthos as indicators of ecological status in coastal brackish waters: a comparative study from the Baltic Sea

A new method for classifying soft-bottom zoobenthic assemblages along the Finnish coasts (northern Baltic Sea) is presented and tested against traditional physicochemical monitoring data in the complex Archipelago Sea. Although multivariate methods for assessing the state of the marine environment have become widely used, few numerical indices can operate over a wide salinity range. We compare indices currently in use and propose a new index, BBI (brackish water benthic index), for the low-saline and species-poor Baltic coastal waters. BBI offers a salinity-corrected tool for classification of the soft-bottom zoobenthos under the demands of the European Union Water Framework Directive.     

Background levels in air of lead,cadmium, mercury and some chlorinated hydrocarbons measured in South Norway

The concentrations of air pollutants were measured during selected periods in late 1974 and early 1975. The observed concentrations were low, comparable to results from similar measurements reported in the literature. This study shows significant time variations in the concentrations of heavy metals, and a clear correlation between the level of these pollutants and the direction of air transport. The lowest concentrations were always observed when air transport was from areas with few sources of pollutants.     

Temporal trends (1990-2000) in the concentration of cadmium, lead and mercury in mosses across Europe

The European heavy metals in mosses survey provides data on the concentration of 10 heavy metals in naturally growing mosses. The survey has been repeated at five-yearly intervals and in this paper we report on the temporal trends in the concentration of cadmium, lead and mercury between 1990 and 2000. Metal- and country-specific temporal trends were observed. In general, the concentration of lead and cadmium in mosses decreased between 1990 and 2000; the decline was higher for lead than cadmium. For mercury not enough data were available to establish temporal trends between 1990 and 1995, but between 1995 and 2000 the mercury concentration in mosses did not change across Europe. The observed temporal trends for the concentrations in mosses were similar to the trends reported for the modelled total deposition of cadmium, lead and mercury in Europe.     

Trophic transfer and accumulation of mercury in ray species in coastal waters affected by historic mercury mining (Gulf of Trieste,northern Adriatic Sea)

Total mercury (Hg) and monomethylmercury (MMHg) were analysed in the gills, liver and muscle of four cartilaginous fish species (top predators), namely, the eagle ray (Myliobatis aquila), the bull ray (Pteromylaeus bovinus), the pelagic stingray (Dasyatis violacea) and the common stingray (Dasyatis pastinaca), collected in the Gulf of Trieste, one of the most Hg-polluted areas in the Mediterranean and worldwide due to past mining activity in Idrija (West Slovenia). The highest Hg and MMHg concentrations expressed on a dry weight (d.w.) basis were found in the muscle of the pelagic stingray (mean, 2.529 mg/kg; range, 1.179–4.398 mg/kg, d.w.), followed by the bull ray (mean, 1.582 mg/kg; range, 0.129–3.050 mg/kg d.w.) and the eagle ray (mean, 0.222 mg/kg; range, 0.070–0.467 mg/kg, d.w.). Only one specimen of the common stingray was analysed, with a mean value in the muscle of 1.596 mg/kg, d.w. Hg and MMHg contents in the bull ray were found to be positively correlated with species length and weight. The highest MMHg accumulation was found in muscle tissue. Hg and MMHg were also found in two embryos of a bull ray, indicating Hg transfer from the mother during pregnancy. The number of specimens and the size coverage of the bull rays allowed an assessment of Hg accumulation with age. It was shown that in bigger bull ray specimens, the high uptake of inorganic Hg in the liver and the slower MMHg increase in the muscle were most probably due to the demethylation of MMHg in the liver. The highest Hg and MMHg contents in all organs were found in the pelagic stingray, which first appeared in the northern Adriatic in 1999. High Hg and MMHg concentrations were also found in prey species such as the banded murex (Hexaplex trunculus), the principal prey of the eagle rays and bull rays, the anchovy (Engraulis encrasicholus) and the red bandfish (Cepola rubescens), which are preyed upon by the pelagic stingray, as well as in zooplankton and seawater. Based on previously published data, a tentative estimation of MMHg bioamagnification was established. The average increase in MMHg between seawater, including phytoplankton, and zooplankton in the Gulf was about 10⁴, and MMHg in anchovy was about 50-fold higher than in zooplankton. The bioaccumulation of MMHg between seawater and small pelagic fish (anchovy) amounted to 10⁶ and between water and the muscle of larger pelagic fish (pelagic stingray) to 10⁷. The MMHg increase between surface sediment and benthic invertebrates (murex) and between benthic invertebrates and small benthic fish was 10². Ultimately, the trophic transfer resulted in a 10³ accumulation of MMHg between water and muscle of larger benthic fish (bull ray, eagle ray, common stingray), suggesting lower bioaccumulation by benthic feeding species.     

Levels of polychlorinated biphenyls, organochlorine pesticides, mercury, cadmium, copper, selenium, arsenic, and zinc in the harbour seal, Phoca vitulina, in Norwegian waters

Residue levels of the chlorinated hydrocarbons polychlorinated biphenyls (PCBs), total DDT, alpha-, beta- and gamma-hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), and oxychlordane in blubber, and the elements mercury, cadmium, copper, selenium, arsenic, and zinc in liver, of 82 harbour seals, Phoca vitulina, were determined. The seals were found dead or dying in Norwegian waters during the disease outbreak caused by a morbilli virus in 1988. Of the chlorinated hydrocarbons, the highest concentrations were found of PCBs, which were 2-4 times higher than the total DDT concentrations. P,p'-DDE was the main contributor to the total DDT, and constituted about 80%. The PCB and total DDT concentrations ranged from 0.4-38 and 0.1-8.8 mg kg(-1), respectively. The mercury concentrations ranged from 0.1-89 mg kg(-1). Significantly higher mean levels of PCBs (13 mg kg(-1) and mercury (16 mg kg(-1)) were found in blubber and liver, respectively, of seals from the Southern coast of Norway, as compared to the corresponding mean levels in seals from the Oslofjord (8.8 and 4.1 mg kg(-1)), and at the Northwestern coast (5.8 and 7.9 mg kg(-1)), respectively. A significant positive correlation was found between the concentrations of selenium and mercury. When the seals were grouped according to sex and age, females of ageclass > 1 and pups of both sexes had significantly lower PCB and total DDT levels than males ageclass > 1. Significantly higher hepatic mercury levels were found in seals ageclass > 1 as compared to pups. Only low levels of the other organochlorines, cadmium and arsenic, were found. Copper and zinc were considered to be present at normal physiological levels. The present organochlorine and heavy metal concentrations gave no support to suggestions that organochlorines and heavy metal pollution may be directly involved in the observed seal deaths.     

Bioaccumulation of lead, mercury, and cadmium in the greater white-toothed shrew, Crocidura russula, from the Ebro Delta (NE Spain): sex- and age-dependent variation

We quantified bioaccumulation of lead, mercury, and cadmium in bones from 105 greater white-toothed shrews (Crocidura russula) collected at the Ebro Delta, a polluted area, and the Medas Islands, a control site. Lead and mercury levels varied with site, age, and sex, although statistical significances depended on each factor. Globally, shrews from the polluted area exhibited significantly higher concentrations of Pb and Hg. Increment of Pb with age was particularly remarkable in wetland animals and was interpreted in relation to human activities, namely hunting. Unlike males, females from the Ebro Delta maintained low Hg levels, which were associated with gestation and lactation. Cadmium levels did not differ between sites, sexes, or ages. This study provides the first data on heavy metals in mammals from this wetland and suggests that C. russula is a good bioindicator of metal pollution. We concluded that sex and age may represent an important source of variation in the bioaccumulation of these metals in wild populations.     

Haematological parameters as predictors of blood lead and indicators of lead poisoning in the black duck (Anas rubripes)

The validity of various haematological parameters as indicators of blood lead concentration and lead poisoning in the black duck (Anas rubripes) is discussed. Elevated (> 40 microg dl(-1)) blood lead (PbB) levels were recorded in 41% of the 229 wild birds examined. No correlation was found between PbB concentration and haematocrit. Zinc protoporphyrin (ZPP) was positively correlated with PbB. Haemoglobin, delta-aminolevulinic acid dehydratase (ALA-d) activity and non-activated/activated ALA-d ratios were negatively correlated with PbB. The minimum PbB levels at which these parameters were affected varied greatly. ZPP and haemoglobin were relatively insensitive to PbB concentrations; whilst ALA-d activity and ALA-d ratio were influenced by PbB concentrations of < 5 microg dl(-1). Log(10) ALA-d ratio was more strongly correlated with PbB (r = -0.953) than log(10) ALA-d activity (r = -0.914) and the predictive validity (% false -ve and +ve predictions) of the ratio method was higher. The high individual variability in ALA-d activities at low PbB levels was greatly reduced by the use of the ALA-d ratio method. The ALA-d ratio method proved the most efficient for screening black duck for lead poisoning in the field.     

Organic matter compounds as source indicators and tracers for marine pollution in a western Mediterranean coastal zone

Introduction  

Complex organic compounds found in oil and sediments linked with a particular source (such as algae, bacteria or vascular plants) are defined as biomarkers and are useful dating indicators in organic geochemistry.     

Accumulation of lead and cadmium in the marine prosobranch Nerita saxtilis, chemical analysis, light and electron microscopy.

The potential value of the marine prosobranch Nerita saxtilis as an efficient biological monitor to heavy metal pollution in the Red Sea was investigated. Storage ability of lead and cadmium was compared in shell, headfoot and digestive gland of the marine snail N. saxtilis collected from Al-Hamrauin area at El-kuseir (lead, 300.35 +/- 28.53 microg/l, 1,716 +/- 16.14. cadmium 20.01 +/- 1.8 microg/l, 161.72 +/- 21.4 mean +/- S.D. for water and sediment, respectively) relative to that of inhabiting marine water and sediment employing atomic absorption spectrometry to determine the organ with highest capability of heavy metal accumulation. The influence of metal storage on light microscopic structure of that organ was investigated. Also, the ultrastructure localization of storage sites in the same organ was determined employing transmission electron microscopy. The digestive gland was shown to accumulate both metals at conccntrations that are several orders of magnitude higher than those in the surrounding marine water. The bioaccumulation capability of lead and cadmium was ranked in the following order; digestive gland > headfoot > shell for lead and digestive gland > shell > headfoot for cadmium. In spite of its evident highest metal storage capability, no histopathological changes were observed in the digestive gland of that marine prosobranch. Enlarged electron dense vesicles and many granules were observed in ultrathin sections in digestive cells of these snails and are suggested to be the sites of storage of detoxified metals. The results of that finding indicate the possibility of using the marine prosobranch N. saxtilis as biomonitor for heavy metal contaminants in the Red Sea.     

Computational spectroscopic study of copper, cadmium, lead and zinc interactions in the environment

Molecular modelling has been used to investigate the interactions of various heavy metals, in order to understand and possibly to control the nature and behaviour of metals, especially in the aquatic environment. The interactions of copper, cadmium, lead and zinc with organic acids were studied using density functional theory (DFT) calculations. Carboxylic acid was used as a model molecule. The structure of each metal carboxylate was optimized and the vibrational spectrum calculated. The results indicate that there is a shift in the calculated v_S(C=O) of metal carboxylates compared with that of carboxylic acid. It was also found that hexaaqua structures of both cadmium and zinc are stable whereas those of copper and lead are not. Furthermore, dipole moment calculations indicate that cadmium carboxylate dihydrate is more representative of cadmium interactions in the aquatic environment. Moreover, hexaaquo cadmium could further interact with surrounding molecules in the aquatic environment.     

Tracking mercury in the southwestern Atlantic Ocean: the use of tuna and tuna-like species as indicators of bioavailability

Mercury is a trace element that is potentially dangerous due its high toxicity and tendency to bioaccumulate in organisms. Currently, high mercury concentrations are seen in the environment especially due climate changes. Studies regarding mercury bioavailability in the southwestern Atlantic Ocean using tuna and tuna-like species are rare. The aim of the present study was to use tuna and tuna-like species (Thunnus atlanticus, Thunnus albacares, Katsuwonus pelamis, Euthynnus alletteratus, Coryphaena hippurus and Sarda sarda) as indicators of the availability of total mercury (THg) in oceanic food webs of the southwestern Atlantic Ocean. THg concentrations varied significantly among species for both muscle and liver (Kruskal–Wallis test; H5,130 = 52.7; p < 0.05; H5,130 = 50.1; p < 0.05, respectively). The lowest concentrations were found in C. hippurus (0.008 mg kg−1 wet weight in the muscle and 0.003 mg kg−1 wet weight in the liver), and the highest concentrations were reported in the muscle of T. atlanticus (1.3 mg kg−1 wet weight) and in the liver of S. sarda (2.5 mg kg−1 wet weight). The continued monitoring of tuna and tuna-like species is necessary to assist in their conservation since tuna can be sentinels of mercury pollution.