Binding forms of toxic heavy metals, mechanisms of entrance of heavy metals into the food chain, and possible measures to reduce levels in foodstuff.

The literature on binding forms of toxic heavy metals is evaluated. In terrestrial ecosystems mercury—with the exception of mushrooms—generally does not enter the food chain in significant quantities, because of its chelation by soil organic matter and its binding to functional groups of cell walls in plant roots. In aquatic ecosystems uptake and accumulation of mercury by organisms occur because of methylation of Hg²⁺ by methylcobalamin produced by microorganisms. Cadmium enters the human food chain mainly via the terrestrial pathway resulting from increasing input into terrestrial ecosystems and its relatively high mobility. In aquatic systems edible molluscs may be a significant source of cadmium because cadmium is concentrated within particulate matter, which is taken up by these organisms. Lead in human diet stems mainly from particles sedimented on food plants containing predominately PbSO₄. Lead is taken up by plants in significant quantities only at relatively high levels in soils and at low pH values. Because of its preferential binding to particulate matter in aquatic ecosystems lead is accumulated in relatively high amounts by certain molluscs especially in contaminated waters.     

Bioaccumulation of selenium (Se) in the Cienega de Santa Clara wetland, Sonora, Mexico

The Cienega de Santa Clara, on the east side of the Colorado River delta, is a brackish wetland supported by agricultural drainage water from the United States that provides habitat for endangered fish and bird species. Bioaccumulation of selenium has created toxicity problems for wildlife in similar wetlands in the United States. This is the first selenium survey in the Cienega de Santa Clara. Ten sites were selected to collect water (dissolved), sediments (total), plants, invertebrates, and fish. Samples were collected from October 1996 to March 1997. Selenium was detected in all samples. Concentrations in water ranged from 5 to 19 microg/L and increased along a salinity gradient. Although water levels of selenium exceeded EPA criterion for protection of wildlife, levels in sediments (0.8-1.8 mg/kg), aquatic plants (0.03-0.17 mg/kg), and fish (2.5-5.1 mg/kg whole body, dry wt) did not exceed USFWS recommended levels. It is concluded from this study that the levels of selenium in water did not affect the overall health of the fish sampled. Therefore, it is important to maintain or improve the water quality entering this wetland to continue to have normal levels of Se in the food chain components.     

Bioavailability of metals and arsenic to small mammals at a mining waste-contaminated wetland

In support of a baseline ecological risk assessment evaluating the impacts of mining wastes at the Milltown Reservoir Sediments Superfund site in Montana, a food chain transfer analysis was performed for resident small mammals. Deer mice (Peromyscus maniculatus) and meadow voles (Microtus pennsylvanicus) were trapped from a 200 A portion of a mixed upland and palustrine wetland, and concentrations of As, Cd, Cu, Pb, and Zn in carcass, liver, kidney, and testes were quantified. Concurrent to small mammal trapping, samples of grasses, forbs, and soils were collected and analyzed for metal and As residues. Using a linear multimedia food-chain model, assuming a forage base of wetland vegetation from the site, ingestion of local surface water, and incidental ingestion of soils with vegetation, body burdens of the metals and As in the herbivores were estimated. As a means of estimating potential element bioavailability at the site, the modeled body burdens were compared with measured element concentrations in herbivore tissues. The analysis indicates that the bioavailabilities of As, Cd, Cu, Pb, and Zn were equal to or less than 0.2% for internal organs and 0.1% for carcasses, on a g/g tissue wet weight basis. Available site data on soil pH, cation exchange capacity, and extractable elements fraction supported the limited release of soil elements. These results suggest that the bioavailable fraction of mining waste metals in riparian wetland soils may be quite small, and, for the Milltown Reservoir site, lower than originally anticipated.     

Effects of Contaminated St. Lucie River Saltwater Sediments on an Amphipod (Ampelisca abdita) and a Hard-Shell Clam (Mercenaria mercenaria)

The St. Lucie estuary (SLE) ecosystem in South Florida has been shown to be contaminated with metals and pesticides. Our earlier studies also showed that aquatic organisms, especially benthic species in the SLE ecosystem, might be potentially at high risk from copper (Cu) exposure. The objectives of this study were to conduct studies with separate groups of organisms exposed to seven field-collected sediment samples from the St. Lucie River according to standard procedures to evaluate toxicity and tissue concentrations of Cu and zinc (Zn). Short term and longer term whole sediment acute toxicity studies were performed with Ampelisca abdita and Mercenaria mercenaria. Analysis of sediment chemical characteristics showed that Cu and Zn are of most concern because their concentrations in 86 % of the sediments were higher than the threshold effect concentrations for Florida sediment quality criteria and the National Oceanic and Atmospheric Administration Screening Quick Reference Tables (SQuiRTs) sediment values. There was no significant effect on survival of the tested organisms. However, increased Cu and Zn concentrations in the test organisms were found. Dry weight of the tested organisms was also inversely related to Cu and Zn concentrations in sediments and organisms. The effects on organism weight and Cu and Zn uptake raise concerns about the organism population dynamics of the ecosystem because benthic organisms are primary food sources in the SLE system and are continuously exposed to Cu- and Zn-contaminated sediments throughout their life cycle. The results of the present study also indicate that Cu and Zn exposures by way of sediment ingestion are important routes of exposure.     

Ecological vulnerability in wildlife: application of a species-ranking method to food chains and habitats

Nature development in The Netherlands is often planned on contaminated soils or sediments. This contamination may present a risk for wildlife species desired at those nature development sites and must be assessed by specific risk assessment methods. In a previous study, we developed a method to predict ecological vulnerability in wildlife species by using autecological data and expert judgment; in the current study, this method is further extended to assess ecological vulnerability of food chains and terrestrial and aquatic habitats typical for The Netherlands. The method is applied to six chemicals: Cd, Cu, Zn, dichlorodiphenyltrichloroethane, chlorpyrifos, and ivermectin. The results indicate that species in different food chains differ in vulnerability, with earthworm-based food chains the most vulnerable. Within and between food chains, vulnerability varied with habitat, particularly at low trophic levels. The concept of habitat vulnerability was applied to a case study of four different habitat types in floodplains contaminated with cadmium and zinc along the river Dommel, The Netherlands. The alder floodplain forest habitat contained the most vulnerable species. The differences among habitats were significant for Cd. We further conclude that the method has good potential for application in mapping of habitat vulnerability.     

Validation of a terrestrial food chain model.

An increasingly important topic in risk assessment is the estimation of human exposure to environmental pollutants through pathways other than inhalation. The Environmental Protection Agency (EPA) has recently developed a computerized methodology (EPA, 1990) to estimate indirect exposure to toxic pollutants from Municipal Waste Combuster emissions. This methodology estimates health risks from exposure to toxic pollutants from the terrestrial food chain (TFC), soil ingestion, drinking water ingestion, fish ingestion, and dermal absorption via soil and water. Of these, one of the most difficult to estimate is exposure through the food chain. This paper estimates the accuracy of the EPA methodology for estimating food chain contamination. To our knowledge, no data exist on measured concentrations of pollutants in food grown around Municipal Waste Incinerators, and few field-scale studies have been performed on the uptake of pollutants in the food chain. Therefore, to evaluate the EPA methodology, we compare actual measurements of background contaminant levels in food with estimates made using EPA's computerized methodology. Background levels of contaminants in air, water, and soil were used as input to the EPA food chain model to predict background levels of contaminants in food. These predicted values were then compared with the measured background contaminant levels. Comparisons were performed for dioxin, pentachlorophenol, polychlorinated biphenyls, benzene, benzo(a)pyrene, mercury, and lead.     

Influence of Mining-Related Activities on Concentrations of Metals in Water and Sediment from Streams of the Black Hills, South Dakota

Water and sediment samples were collected from streams in Spearfish Creek, Whitewood Creek, and Bear Butte Creek watersheds in the Black Hills, SD, an area impacted by gold mining operations. Arsenic concentrations that exceeded the U.S. Environmental Protection Agency's Maximum Concentration Limit of 50 microg/L for drinking water were found in water from Annie Creek, a tributary of Spearfish Creek, and from Whitewood Creek. Gold Run, a tributary of Whitewood Creek, and Annie Creek contained Se concentrations in water that exceeded the EPA Ecotox threshold of 5 microg/L and were classified as a high hazard for Se accumulation from water into the planktonic food chain and for resultant toxicity to fish and aquatic birds. Concentrations of As, Cd, Cu, Hg, Ni, Pb, and Zn in sediment exceeded EPA Ecotox thresholds in one or more of the watersheds suggesting potential adverse ecological effects. Sediment from Rubicon Creek, a tributary of Spearfish Creek, contained Se concentrations high enough (4.0 microg/g) to be a moderate hazard for accumulation from sediments into the benthic food chain, with resultant dietary toxicity to fish and aquatic birds. These results are discussed in light of historical mining activities and recent clean-up and reclamation efforts. Based on the results and comparisons to Ecotox tresholds, further studies of ecological effects are warranted.     

Mercury Concentrations in Nestling Wading Birds Relative to Diet in the Southeastern United States: A Stable Isotope Analysis

Mercury (Hg) is a ubiquitous environmental contaminant that is transferred trophically through aquatic and terrestrial food webs. To better understand the routes of Hg uptake in organisms that rely on both aquatic and terrestrial food resources, we analyzed feather and down samples from nestling wading birds of varying trophic positions in both inland and coastal colonies. We used stable nitrogen and carbon isotope analyses to evaluate trophic positions of individual species (δ(15)N) and differences in foraging habitat use (δ(13)C). Inland, aquatic species had higher trophic status than the single terrestrial species examined, and the expected positive relationship between δ(15)N and Hg content of feathers was observed. However, the same was not true for all species from coastal colonies. Feathers from species that primarily consumed saltwater prey were relatively high in δ(15)N value and low in Hg content, which is opposite of the trend expected due to Hg biomagnification in food chains. In contrast, coastal species foraging in freshwater or a combination of freshwater and saltwater habitats displayed greater Hg contents in feathers. The apparent differential use of the two aquatic systems (freshwater and saltwater) in coastal environments by wading bird species results in variations in δ(15)N values and Hg contents in nestling feathers not found in species associated with only freshwater systems.     

Predicting metal uptake by wetland plants under aerobic and anaerobic conditions

Metal pollution can be a serious threat to ecosystems at a global scale. Although the bioavailability of potentially toxic metals is determined by many biotic and abiotic factors, including pH and redox potential, total metal concentrations in the soil are used widely to assess or predict toxicity. In the present study we tested the effect of desiccation of soils differing in acidification potential and total heavy metal contamination on the growth and metal uptake of three typical, common wetland species: Caltha palustris, Juncus effusus, and Rumex hydrolapathum. We found that plant growth in wet soils mainly was determined by nutrient availability, though in dry soils the combined effects of acidification and increased metal availability prevailed. Metal uptake under anaerobic conditions was best predicted by the acidification potential (sediment S/[Ca + Mg] ratio), not by total metal concentrations. We propose that this is related to radial oxygen loss by wetland plant roots, which leads to acidification of the rhizosphere. Under aerobic conditions, plant metal uptake was best predicted by the amount of CaCl2-extractable metals. We conclude that total metal concentrations are not suitable for predicting bioavailability and that the above diagnostic parameters will provide insight into biogeochemical processes involved in toxicity assessment and soil policy.     

Effects of metal-contaminated forest soils from the Canadian shield to terrestrial organisms

The effects of elevated metal concentrations in forest soils on terrestrial organisms were investigated by determining the toxicity of six site soils from northern Ontario and Quebec, Canada, using a battery of terrestrial toxicity tests. Soils were collected from three sites on each of two transects established downwind of nickel (Sudbury, ON, Canada) and copper (Rouyn-Noranda, PQ, Canada) smelting operations. Site soils were diluted to determine if toxicity estimates for the most-contaminated site soils could be quantified as a percent of site soil. Rouyn-Noranda soils were toxic following acute exposure (14 d) to plants, but not to invertebrates (7 d for collembola and 14 d for earthworms). However, Rouyn-Noranda soils were toxic to all species following chronic exposure (21, 35, and 63 d for plants, collembola, and earthworms, respectively). The toxicity of the Rouyn-Noranda site soils did not correspond to the gradient of metal concentrations in soil. Metal-contaminated Sudbury soils were toxic to plants but not to invertebrates, following acute exposure. Chronic exposure to Sudbury soils caused adverse effects to plant growth and invertebrate survival and reproduction. The toxicity of Sudbury soils corresponded to the metal concentration gradient, with one exception: The reference soil collected in October was toxic to collembola following acute and chronic exposure. This study evaluated the applicability of the new Environment Canada terrestrial toxicity test methods, developed using agricultural soils, to forest soils and also provided useful data to assess the ecological risk associated with mixtures of metals in soil.     

Ecological risk assessment of contaminated soils through direct toxicity assessment

A microcosm (MS-3) with a multispecies soil system is introduced as an experimental tool for direct toxicity assessment of contaminated soils. The capacity of MS-3 to determine soil ecotoxicity potential was evaluated using samples from three sites contaminated with organic and/or inorganic compounds. Soils were toxic to soil-dwelling organisms (earthworm, plants, and microorganisms) and to aquatic organisms (algae and RTG-2 cell fish). As expected, responses varied substantially among different soils and organisms. The application of this evaluation system provided complementary information to the chemical characterization. For soils containing metals the toxic response was lower than predicted from total metal concentrations. For hydrocarbons, the toxicity response agreed with estimated values. The induction of EROD activity suggested the presence of dioxin-like compounds, which had not been addressed in the chemical characterization. The proposed multispecies system affords the measurement of 11 endpoints covering three soil and three aquatic taxonomic groups, reproduces soil conditions and gradients, and appears as an excellent complementary tool to chemical analysis for characterization of contaminated sites.     

Residue of organochlorine compounds and mercury in birds' eggs from the Niagara Peninsula,Ontario

Eggs (307) were collected in 1971 from twenty species of birds with a variety of feeding habits from the Niagara Peninsula. This area of Ontario is intensively developed for agriculture and heavy industry and has a large urban population. Representative species were obtained from both the terrestrial and aquatic food chains. Eggs were analyzed for organochlorine insecticides, polychlorinated biphenyls, and total mercury. Eggs from carnivorous species at the top of the aquatic food chain had the highest mean residues of DDT (7.6 to 22.4 ppm), PCB (3.5 to 74.0 ppm) and total mercury (0.64 to 0.83 ppm). Eggs from some terrestrial carnivores (red-tailed hawk and great horned owl) also had relatively high residues (2.5 to 3.9 ppm of DDT, 0.2 to 1.0 ppm of PCB, 0.06 to 0.09 ppm of mercury), however levels were much lower than those found in eggs from aquatic-feeding carnivores. Eggs from one red-shouldered hawk had residues comparable to the aquatic feeding carnivores. Eggs from herbivorous and insectivorous birds of both aquatic and terrestrial environments contained much lower residues. PCB residues were slightly lower in eggs among the terrestrial feeding species (0.05 to 2.0 ppm) than among the aquatic feeders (0.14 to 4.0 ppm) and tended to be lower in eggs from terrestrial species collected in rural than in city environs. Levels of DDT were similar in both groups with eggs from terrestrial feeders containing mean residues between 0.15 and 2.64 ppm and those from aquatic feeders between 0.33 and 2.79 ppm.     

Short-term ecological risks of depositing contaminated sediment on arable soil

Sediments act as sinks of suspended material from surface water. Dredging of regional waters and subsequent disposal of the sediment on soil may lead to contamination of the soil, in some cases resulting in exceedance of soil quality standards. Soil quality standards are based on total concentrations. Total levels, however, do not always give an indication of adverse effects in soil ecosystems. Instead, truly bioavailable concentrations should be used as indicators. In this study we aim to test a set of suited indicators. We carried out partition and accumulation assays with metals and polycyclic aromatic hydrocarbons (PAHs) in soils and mixtures of soil and sediment, as well as a limited number of toxicity bioassays. We also investigated the rate of disappearance of PAHs from mixtures of sediments and soils. The experiments confirm that total levels indeed are not indicative of truly occurring toxic effects: mixing of highly contaminated sediments with soil hardly gave rise to either additional accumulation of metals and PAHs or excess toxicity. This indicates that the bioavailability of the metals and PAHs present in the sediment is limited. This general finding is confirmed by the low rate of disappearance of PAHs from the mixtures. It is concluded that inclusion of the aspects of bioavailability, mixture toxicity, and degradation, in the way described in this report, will solve the major limitations of the current methodology of classification of contaminated sediments.     

Heavy metal toxicity to microbe-mediated ecologic processes: a review and potential application to regulatory policies

Microorganisms are sensitive to heavy metal pollution as are other components of the biota. However, most studies on the interactions between microbes and heavy metals have been conducted in synthetic media or in altered (e.g., sterilized) environmental samples and usually have used only single species. Few studies have evaluated the effects of heavy metals on the activities of natural heterogeneous microbial populations, both autotrophic and heterotrophic, in terrestrial and aquatic environments. These latter studies have shown that heavy metals inhibit primary productivity, nitrogen fixation, the mineralization of carbon, nitrogen, sulfur, and phosphorus, litter decomposition, and enzyme synthesis and activity in soils, sediments, and surface waters. The potential adverse effects of heavy metals on such microbe-mediated ecologic processes need to be incorporated into the methodologies used by regulatory agencies, such as the U.S. Environmental Protection Agency, to prepare environmental risk assessments which, in turn, are used to formulate environmental criteria, such as the Water Quality Criteria, and to evaluate the safety to the environment of exposure to "new chemical substances," as mandated by the U.S. Toxic Substances Control Act of 1976. To provide appropriate data that can be assimilated into regulatory policy, it is essential that microbial ecotoxicity tests be standardized, are neither costly nor difficult to train personnel to conduct, and produce data that can be quantitated.     

Transfer of Heavy Metals Through Three Components: Sediments,Plants and Fish in the Area with Previous Mining Activity

This study aims to evaluate the ecological risk and distribution of heavy metals in sediment, plants and fish in a seriously polluted water reservoir in Krompachy, Slovakia. Special attention was given to the different food web positions of individual fish species (predators, omnivores) and their size. The degree of heavy metal contamination in sediments decreased in the order Cu > Pb > Cr > Hg > Cd, and their mutual proportion was largely consistent with concentrations found in aquatic plants, i.e. water sedges (Carex acutiformis). Of the seven fish species investigated, piscivorous perch (Perca fluviatilis) accumulated higher quantities of metal than fish situated at lower trophic levels. Interestingly, co-equal levels of heavy metals to those found in perch (P. fluviatilis) also occurred in rudd (Scardinius erythrophthalmus). The Hg values in some fish muscles exceeded the maximum permissible limits suggesting a persistent problem of old environmental burden from former mining activities.

     

In situ and laboratory bioassays with Chironomus riparius larvae to assess toxicity of metal contamination in rivers: the relative toxic effect of sediment versus water contamination

We used bioassays employing head capsule width and body length increase of Chironomus riparius larvae as end points to evaluate metal contamination in streams. Bioassays were performed in situ near an abandoned Portuguese goldmine in the spring of 2003 and 2004. Bioassays also were performed under laboratory conditions with water and sediment collected from each stream to verify if laboratory bioassays could detect in situ toxicity and to evaluate the relative contribution of sediment and water to overall toxicity. We used field sediments with control water and control sediments with field water to discriminate between metal contamination in water and sediment. Field water with dry and sieved, organic matter-free, and nontreated sediments was used to determine the toxicity of heavy metals that enter the organism through ingested material. In both in situ and laboratory bioassays, body length increase was significantly inhibited by metal contamination, whereas head capsule width was not affected. Body length increase was more affected by contaminated sediment compared to contaminated water. The lowest-effect level of heavy metals was observed in the dry and sieved sediment that prevented ingestion of sediment particles by larvae. These results suggest that body length increase of C. riparius larvae can be used to indicate the impact of metal contamination in rivers. Chironomus riparius larvae are more affected by heavy metals that enter the organism through ingested sediment than by heavy metals dissolved in the water column. Nevertheless, several factors, such as the particle size and organic matter of sediment, must be taken into account.     

Sensitivity of mottled sculpins (Cottus bairdi) and rainbow trout (Onchorhynchus mykiss) to acute and chronic toxicity of cadmium, copper, and zinc

Studies of fish communities of streams draining mining areas suggest that sculpins (Cottus spp.) may be more sensitive than salmonids to adverse effects of metals. We compared the toxicity of zinc, copper, and cadmium to mottled sculpin (C. bairdi) and rainbow trout (Onchorhynchus mykiss) in laboratory toxicity tests. Acute (96-h) and early life-stage chronic (21- or 28-d) toxicity tests were conducted with rainbow trout and with mottled sculpins from populations in Minnesota and Missouri, USA, in diluted well water (hardness = 100 mg/L as CaCO3). Acute and chronic toxicity of metals to newly hatched and swim-up stages of mottled sculpins differed between the two source populations. Differences between populations were greatest for copper, with chronic toxicity values (ChV = geometric mean of lowest-observed-effect concentration and no-observed-effect concentration) of 4.4 microg/L for Missouri sculpins and 37 microg/L for Minnesota sculpins. Cadmium toxicity followed a similar trend, but differences between sculpin populations were less marked, with ChVs of 1.1 microg/L (Missouri) and 1.9 microg/L (Minnesota). Conversely, zinc was more toxic to Minnesota sculpins (ChV = 75 microg/L) than Missouri sculpins (chronic ChV = 219 microg/L). Species-average acute and chronic toxicity values for mottled sculpins were similar to or lower than those for rainbow trout and indicated that mottled sculpins were among the most sensitive aquatic species to toxicity of all three metals. Our results indicate that current acute and chronic water quality criteria for cadmium, copper, and zinc adequately protect rainbow trout but may not adequately protect some populations of mottled sculpins. Proposed water quality criteria for copper based on the biotic ligand model would be protective of both sculpin populations tested.     

Content of Metals in Compartments of Ecosystem of a Siberian Pond

During three field seasons (June–September) of 1997–99 contents of Na, K, Ca, Mg, Fe, Mn, Zn, Cu, Al, Cr, Ni, Cd, and Pb were determined in compartments of ecosystem (surrounding soils, bottom sediments, water, zoobenthos, macrophytes, and fish) of a fish and recreation pond situated at the edge of Krasnoyarsk City (Siberia, Russia). Contents of most parts of metals in soils, water, and macrophytes significantly correlated with each other. As concluded, their contents were determined by natural, general, geochemical peculiarities of the region. Heavy metals, contents of which were higher than federal upper limits of concentration, were revealed. In muscles of fish with different feeding spectra—crucian and perch—concentrations of some metals differed significantly; correlation graphs for metals also had different structures. Comparison of our data with those on diverse aquatic ecosystems of Siberia, Europe, North America, and China published in the last decade was carried out. It was concluded that a distribution of heavy metals in the compartments of an aquatic ecosystem presently have to be determined for each particular water body until general regularities are discovered. Received: 22 August 2000/Accepted: 22 February 2001     

Aquatic toxicity of nitrogen mustard to Ceriodaphina dubia, Daphnia magna, and Pimephales promelas

Investigation of toxicity of mustard compounds to aquatic organisms has been limited although their effects on terrestrial mammal species have been well studied. In this study, the 48-h LC50 values of nitrogen mustard (HN2) are reported for two aquatic invertebrate species (Daphnia magna and Ceriodaphnia dubia) and for one fish species (Pimephales promelas). Mean LC50 values to C. dubia, D. magna, and P. promela were 1.12, 2.52, and 98.86 mg/L, respectively. C. dubia was the species most sensitive to HN2. Seven-day lethal and sublethal tests with P. promelas and C. dubia were also conducted. In chronic tests, fathead minnow growth was significantly reduced by 2.50 mg/L HN2, while C. dubia reproduction was significantly affected by 7.81 mug/L HN2. These adverse effects on aquatic organisms caused by lower-level concentrations of HN2 indicate that a possible aquatic ecosystem disaster could occur either after a chemical spill or during chemical warfare.     

Contamination Level and Spatial Distribution of Heavy Metals in Water and Sediments of El Guájaro Reservoir,Colombia

Heavy metals have become a subject of special concern worldwide, mainly due to high persistence in the environment, toxicity, biogeochemical recycling and ecological risk. Therefore, the objective of this investigation was to analyze the spatial–temporal distribution of heavy metals in water and sediments to determine the environmental status of El Guájaro Reservoir, where such studies have not been developed. Two measurement campaigns (dry and wet period) were carried out and eight sampling stations were selected. A comparison of water and sediment quality parameters with existing national and international regulations was done. Also, heavy metal distribution maps were generated, and the geoaccumulation index was calculated to identify sources and sediments contamination level. Based on the obtained results, agriculture and mining activities are the main causes of the reservoir contamination. This metals levels could be a potential risk for the aquatic life and the populations that are supplied from this water body.