Progress of research on the toxicology of antibiotic pollution in aquatic organisms

Antibiotics are widely used to improve human and animal health and treat infections. Antibiotics are often used in livestock farms and fisheries to prevent diseases and promote growth. Recently, there has been increasing interest in the presence of antibiotics in aquatic environments. Low levels of antibiotic components are frequently detected in surface water, seawater, groundwater, and even drinking water. Antibiotics are consistently and continually discharged into the natural environment as parent molecules or metabolites, which are usually soluble and bioactive, and this results in a pseudo and persistent pollution. The effects of environmental antibiotic toxicity on non-target organisms, especially aquatic organisms, have become an increasing concern. Although antibiotics have been detected worldwide, their ecological and developmental effects have been poorly investigated, particularly in non-target organisms. This review describes the toxicity and underlying mechanism of antibiotic contamination in aquatic organisms, including the effects on vertebrate development. A considerable number of antibiotic effects on aquatic organisms have been investigated using acute toxicity assays, but only very little is known about the long-term effects. Aquatic photosynthetic autotrophs, such as Pseudokirchneriella subcapitata, Anabaena flos-aquae, and Lemna minor, were previously used for antibiotic toxicity tests because of low cost, simple operation, and high sensitivity. Certain antibiotics show a different degree of potency in algal toxicity tests on the basis of different test algae. Antibiotics inhibit protein synthesis, chloroplast development, and photosynthesis, ultimately leading to growth inhibition; some organisms exhibit growth stimulation at certain antibiotic concentrations. Daphnia magna and other aquatic invertebrates have also been used for checking the toxicity priority of antibiotics. When investigating the acute effect of antibiotics (e.g., growth inhibition), concentrations in standard laboratory organisms are usually about two or three orders of magnitude higher than the maximal concentrations in the aquatic environment, resulting in the underestimation of antibiotic hazards. Vertebrate organisms show a promising potential for chronic toxicity and potentially subtle effects of antibiotics, particularly on biochemical processes and molecular targets. The adverse developmental effects of macrolides, tetracyclines, sulfonamides, quinolones, and other antibiotic groups have been evaluated in aquatic vertebrates such as Danio rerio and Xenopus tropicalis. In acute toxicity tests, low levels of antibiotics have systematic teratogenic effects on fish. The effects of antibiotics on oxidative stress enzymes and cytochrome P450 have been investigated. Cytotoxicity, neurotoxicity, and genotoxicity have been observed for certain antibiotic amounts. However, there are no firm conclusions regarding the chronic toxicity of antibiotics at environmentally relevant levels because of the lack of long-term exposure studies. Herein, future perspectives and challenges of antibiotic toxicology were discussed. Researchers should pay more attention to the following points: chronic toxicity and potentially subtle effects of environmentally relevant antibiotics on vertebrates; effects of toxicity on biochemical processes and mode of action; combined toxicity of antibiotics and other antibiotics, metabolites, and heavy metals; and environmental factors such as temperature and pH.     

伊维菌素在环境中的降解及其对七种水生生物的急性毒性研究

伊维菌素作为一种高效的抗寄生虫兽药,在畜禽业有着广泛的应用。但药物随着畜禽动物的代谢产物的排放而进入自然生态系统也成为逐渐显现的环境问题。由于药物具有在自然环境中难以快速降解和对水生枝角类高毒性的特点,因此流入天然水体的伊维菌素存在着影响水生态平衡的风险。为了比较全面评估药物对水生动物潜在的毒害作用,研究模拟天然河道环境,对药物在底质中的降解速率进行了测定,并选取7种占据不同生态位的水生生物作为试验对象,通过关于急性毒性的国家标准试验方法来初步评价药物对水生态系统的风险。结果显示伊维菌素在自然水体中降解缓慢,在泥水混合25℃恒温条件下,70d的降解率仅为28.3%。急性毒性试验结果显示伊维菌素对发光细菌(Photobacterium)并不表现出毒性,对淡水小球藻(Chlorella vulgaris)的96h EC50=19.80 mg/L,属中毒;而对其他实验生物则表现出了较高的毒性,伊维菌素对斑马鱼(Brachydanio rerio)、食蚊鱼(Gambusia affinis)和鲫鱼鱼苗(Carassius carassius)的96h LC50分别为40.48、34.81和13.79μg/L,对罗氏沼虾(Macrobrachium rosenbergii)的96h LC50=7.87μg/L,对大型溞(Daphniamagna)的24h LC50=4.81 ng/L,均属极高毒。因此残留在天然水体的伊维菌素对水生态中的生物有较大影响,对含伊维菌素的废弃物排放进行监控和科学管理非常必要。     

乙腈的水生态基准

本文参照美国国家环保局推荐的“推导保护水生生物及其用途的国家水质基准的技术指南”,根据我国水生生物区系特点,通过水生生物毒性试验研究和制定石油化工废水中重要污染物—乙腈的水生态基准。试验动物涉及到4个门、6个纲、8个科、13属和13个种。文中根据乙腈对13种水生动物的急性毒性试验,对水生动物的慢性毒性试验以及对水生植物浮萍的生长抑制试验,推导出乙腈的基准连续浓度为413mg／L,基准最大浓度为1145mg／L。     

Influence of water temperature and waterborne cadmium toxicity on growth performance and metallothionein–cadmium distribution in different organs of Nile tilapia,Oreochromis niloticus (L.)

Cadmium (Cd) is believed to be one of the most abundant and ubiquitously distributed toxins in the aquatic system. This metal is released to the aquatic environment from both anthropogenic sources, such as industrial, agricultural and urban effluents as well as natural sources, such as rocks and soils. Otherwise, the temperature increase of water bodies, which has been observed due to global climatic changes, has been shown to increase Cd toxicity for several aquatic animal species including fish. In the present study, Nile tilapia, Oreochromis niloticus (L.), (26.0±0.38 g) were reared at 20, 24, 28, or 32 °C and exposed to 0.0 or 0.5 mg Cd/L for 8 weeks to investigate effects of water temperature, Cd toxicity and their interaction on fish performance as well as metallothionein (MT) and Cd distribution in different fish organs. It was found that fish reared in Cd-free group at 28 °C showed the optimum growth and feed intake, while Cd-exposed fish showed low growth and feed intake irrespective to water temperature. A synergetic relationship between water temperature and Cd toxicity was observed where Cd toxicity increased as water temperature increased and the worse growth was obtained in Cd-exposed fish reared at 32 °C. Additionally, the highest Cd residues in different fish organs were detected in Cd-exposed fish reared at 32 °C. Similarly, MT concentrations in different fish organs increased as water temperature increased especially in Cd-exposed fish groups. A high positive correlation between MT and Cd concentrations in fish organs was detected. The distribution of MT and Cd levels was in the order of liver>kidney>gills>muscles. The present study revealed that the optimum water temperature suitable for Nile tilapia growth is 28 °C. Additionally, Cd exposure had a deteriorate effect on the growth and health of Nile tilapia. This hazardous effect increased as water temperature increased. Further, liver and kidney were the prime sites of Cd accumulation, while Cd load in the muscles was the lowest as compared to the other investigated organs.     

Toxicological Considerations of Contaminants in the Terrestrial Environment for Ecological Risk Assessment

The terrestrial environment acts as a “sink” for contaminants that have been purposely or accidentally released into the environment. Science and policy that support protective measures for terrestrial ecosystems have run behind those of aquatic toxicology and water quality concerns. As a result ecological risk assessment (ERA) involving terrestrial environments tends to be conducted at a simplistic level, relying on numeric targets (soil quality criteria) as a basis for decision-making. However, soil criteria for ecological receptors are somewhat deficient in terms of the numbers available and the data that supports these numbers. Direct toxicity assessments (DTA) for terrestrial environments, such as those used for water quality evaluations, can provide additional useful information about the toxicity and bioavailability of mixtures of contaminants present in soils. This article outlines the approaches used for assessing the toxicity of soil contaminants in terrestrial environments and critiques their advantages and pitfalls.     

A review of boron effects in the environment

Boron (B) is a naturally occurring element that is found in the form of borates in the oceans, sedimentary rocks, coal, shale, and in some soils. Borates are released naturally into the atmosphere and aquatic environment from oceans, geothermal steams, and weathering of clay-rich sedimentary rocks. B is also released to a lesser extent from anthropogenic sources. B concentrations in air range from <0.5 to 80 ng/m³ with an average of 20 ng/m³, and in soils from 10 to 300 mg/kg with an average of 30 mg/kg. Concentrations of B in surface freshwaters are typically < 0.1–0.5 mg/L; much higher concentrations are measured in a few areas, depending on the geochemical nature of the drainage catchment. B accumulates in both aquatic and terrestrial plants, but it does not appear to be biomagnified through the food chain. No observed effect concentrations (NOECs) for aquatic invertebrates tend to be in the range of 6–10 mg B/L with lower values of 1–2 mg/L for community studies. No effect concentrations for fish in natural waters are around 1 mg/L, although lower values have been recorded in reconstituted water. Comparing no effect concentrations with the general ambient environmental levels indicates that the risk to aquatic ecosystems from B is low. In a few B-rich areas, natural levels will be higher; however, there is some indication that organisms may be Actapted to the local conditions. B is an essential micronutrient for higher plants with interspecies differences in the levels required for optimum growth. In general, there is a small concentration range between deficiency and toxicity; however, toxicity owing to excess B is much less common in the environment than B deficiency. Levels of B in aquatic plants growing in areas receiving B-rich runoff from irrigated fields are higher than dietary concentrations, which cause effects on the growth of young birds in the laboratory; however, the bioavailability in the field of such plant-accumulated B is uncertain.     

大沽排污河生态修复河道水质综合评价及生物毒性影响

为了改善城市河道水质,实现排污河污染控制与修复,在天津市大沽排污河的上游代表性河段开展了河道原位生态修复工程示范。对植物修复后河道的污染状况进行了监测和分析,与清洁河道做了比较,并对水质修复效果和生物毒性影响状况进行综合分析和评价,研究生态修复示范工程对排污河水质的修复效果和生态效应。结果表明:经种植水葱等水生植物进行生态修复后,河道污染一定程度上降低,水质得到改善。大沽河主要污染是营养元素N、P污染和有机物污染,重金属污染不严重。植物修复对电导率、溶解性总固体(TDS)、盐度、氯化物有一定影响,但影响不显著;对COD等有机污染的修复效果较好,最高去除效率可达54%,但相比清洁水域值依然较高,有机污染依然较严重;对营养元素N、P没有修复效果,反而修复区有升高的趋势,相对清洁水域污染严重。主成分分析表明水质参数主要是氨氮、总氮、总磷代表的营养元素及pH值、DO、电导率、TDS、盐度和氯化物,综合评定结果显示修复区域芦苇根部水质最好;聚类分析将17个水质指标分成5类,并与主成分分析结果显示出一致性。植物根际周边的微生物数量多,群落多样性高。植物修复对水样植物毒性影响明显,能降低其毒性;水样对发光菌均具有毒性作用,存在潜在的急性生物毒性;修复区水样对水生动物大型蚤不存在急性生物毒性。     

Rationale and Procedures for Using the Tissue-Residue Approach for Toxicity Assessment and Determination of Tissue,Water, and Sediment Quality Guidelines for Aquatic Organisms

This article describes a set of procedures for developing tissue, water, and sediment quality guidelines for the protection of aquatic life by using the tissue-residue approach (TRA) for toxicity assessment. The TRA, which includes aspects of the Critical Body Residue (CBR) approach, associates tissue concentrations of chemicals with adverse biological effects in a dose-response fashion that can be used to determine CBRs. These CBRs can then be used to develop tissue quality guidelines (TQGs), which may be translated into water or sediment guidelines with bioaccumulation factors. Not all toxicants are amenable to this type of analysis; however, some appear to exhibit relatively consistent results that can likely be applied in a regulatory framework. By examining tissue residues, variations in toxicokinetics (temporal aspects of accumulation, biotransformation, and internal distribution) are greatly reduced allowing a greater focus on toxicodynamics (action and potency) of the toxicants. The strongest feature of this approach is causality; hence, guidelines based on tissue concentrations are based on data demonstrating a causal relationship between the acquired dose and the biological effect. Because the TRA has utility for assessing the toxicity of contaminant mixtures, an approach is presented here using toxic unit values that can be used to assess the likelihood of observing toxic effects based on tissue residues.     

Effect of hardness on bioavailability and toxicity of cadmium to rainbow trout

Abstract

Water quality characteristics affecting toxicity of metals to aquatic life include pH, inorganic and organic ligands (negatively charged ions and molecules), and water hardness. Ligands control the ability of natural waters to bind metals which could adversely affect aquatic life. Bioavailability of metals in natural waters is primarily controlled by alkalinity. Hardness does not affect metal complexation but can reduce acute toxicity through antagonistic mechanisms. In most natural waters, concentrations of alkalinity and hardness are similar, but they may be very different in some waters.

Most toxicity studies have not distinguished between reduced toxicity resulting from effects of hardness and that resulting from complexation of metals by ligands. A series of acute and long-term experiments were conducted to assess these relationships while exposing rainbow trout (Oncorhynchus mykiss) to cadmium (Cd) in waters of low alkalinity (30 mg L^?1) and hardnesses of 400, 200, and 50 mg L^?1 adjusted with magnesium sulfate (MgSO⁴). These tests did not show a strong antagonistic influence of Mg hardness on Cd toxicity. At Mg hardnesses of 50, 200, and 400 mg L^?1, 96-h LC50s were 3.02, 6.12, and 5.70 μg Cd L^?1, differing by a factor of only 1.8. Similarly, chronic values derived from 100-day experiments in waters with the same range of hardness were 1.47, 3.57, and 3.64 μg L^?1, respectively. With an eight-fold difference in Mg hardness, chronic values differed by a factor of only 2.5. Antagonistic properties of hardness are primarily controlled by Ca with Mg playing a minor role. The long-term role of Ca in reducing metal toxicity will require further investigation.     

在培养基和食料中添加铅和镉对轮虫种群动态的影响

由于工业活动的影响,墨西哥水体环境中的重金属浓度在上升.浮游动物,尤其是轮虫类,由于对环境变化十分敏感而且是淡水中的常见组成部分,因此被广泛用于生态毒理试验以确定水质标准.在不同的胁迫途径下(如通过培养基或食料),重金属的毒性是不同的.在本研究中,通过在轮虫Brachionus rubens的培养基和食料中添加重金属这两种途径,我们评估了镉和铅的效应.对于这两种重金属,均采用将轮虫置于含0.5×106个/ml绿藻的培养基中或每天喂食经5倍于LC50值的金属处理(1,2和4h)的绿藻.对于在培养基中添加镉,使用了三个毒性水平(0.1,0.2和0.4 mg/L),铅的浓度分别为0.005,0.010 和0.015 mg/L.基于LC50的数据,B.rubens对铅的敏感性要比镉高24倍.镉浓度为0.4 mg/L时,培养基中加入镉造成B.rubens的生长趋缓.而喂食经不同时间处理的绿藻后,轮虫的密度随着食料在重金属中处理时间的延长而减小.培养基中或食料中添加铅时,轮虫种群生长的的趋势与在镉处理下的情况类似.随着培养基中重金属浓度的增加,每天种群增长率(r值)会减小.在培养基和食料处理两种不同途径下,r值会在0.33(对照)到0.02 d-1(经重金属处理)间变化[动物学报 51(1)46-52,2005].     

Enantioselective toxicity of metolachlor to Scenedesmus obliquus in the presence of cyclodextrins

Cyclodextrins (CDs) possess a variety of chiral centers and are capable of recognizing enantiomeric molecules through the formation of inclusion complexes. Two types of CDs, α-cyclodextrin (α-CD) and β-cyclodextrin (β-CD), were selected to evaluate the effects of the enantioselective ecotoxicity of racemic metolachlor (Rac-metolachlor) and its S-enantiomer (S-metolachlor) on the freshwater algae Scenedesmus obliquus (S. obliquus) by acute toxicity test. The results showed that the aquatic toxicity of S-metolachlor was higher than Rac-metolachlor and that CDs enhanced the toxicity of metolachlor enantioselectively by increasing the aquatic toxicity of Rac-metolachlor rather than that of S-metolachlor to S. obliquus. The equilibrium constant for Rac-metolachlor-CD complexes was higher than that of S-metolachlor-CDs, which was responsible for the greater aquatic toxicity shift effect of Rac-metolachlor. Thermodynamic studies of CD complexes showed that inclusion for all of the complexes was primarily a spontaneous, enthalpy-driven process. These results will help to understand the preliminary mechanism of shifting aquatic toxicity of metolachlor by CDs and the CDs mediated environmental processes of metolachlor, to correctly apply CDs to chiral pesticides formulation and environmental remediation of chiral contaminants.     

Altered toxicities of fatty acid salts in green paramecia cultured in different waters

Detergents including fatty acid salts act as surface-active agents and thus possibly damage the plasma membrane structures of aquatic organisms. Therefore, when excess, the house-used and industrial outflows of such detergents into aquatic environments may have considerable impacts on the ecosystem. In this study, we propose the use of green paramecia (Paramecium bursaria) for assessing the acute toxicity of eight fatty acid salts (Na and K salts of oleate, palmitate, laurate and myristate) under various water conditions. The Paramecium in the stationary phase were used for a toxicity assay carried out on 12-well microplates and the median lethal concentration (LC50) was determined for each fatty acid salt. In the low mineral culture medium prepared with ultra-pure water, the LC50 for each fatty acid ranged from 5.8 to 144 ppm (w/v). The toxic levels of fatty acid salts differed in the following order: laurate, myristate > or = oleate, palmitate. The toxic levels of oleate and palmitate salts were ca. 10-fold lower than those of laurate and myristate salts. When river water and local tap water instead of ultra-pure water were used for culturing, the toxic levels of all fatty acid salts were drastically lowered compared to the low mineral condition by 30- to 100-fold (198-660 ppm, w/v). Similar detoxification effect was observed when Ca or Mg was added to the low mineral culture media, indicating that the toxicity of fatty acid salts can be notably lowered as the mineral content increases. As we demonstrated that toxicities of fatty acid salts can be lowered in river water and tap water compared to the low mineral condition, some chemical substances behave differently in the different water conditions. Therefore, the use of natural waters reflecting the real environmental conditions in further collection of data on the ecotoxicity impacts of variety of chemicals is highly encouraged.     

Comparison of the Acute Toxicity of Corexit 9500 and Household Cleaning Products

Surfactant formulations used in chemical dispersing agents are derived from the same functional components used in numerous household products such as dishwashing soaps and laundry detergents. During the Deep Water Horizon (DWH) oil spill response, a significant volume of chemical dispersant was deployed, causing members of the public and the media to question the role of chemical dispersant (Corexit 9500) usage in mitigating oil spill effects. Consequently, laboratory tests were conducted by regulatory agencies to further evaluate and substantiate the existing aquatic toxicity of Corexit dispersants. To help put dispersant toxicity in context, two independent accredited labs were commissioned to conduct parallel studies that compared the acute toxicity of Corexit 9500 to common household cleaning agents. The results indicate that the acute toxicity of Corexit 9500 to marine aquatic organism is either within the median range or less toxic than the household cleaning agents tested. The median LC50 value for Corexit 9500 exposures to Americamysis bahia was 42.5 mg/L (four products were less toxic and four products were more toxic); whereas, the median LC50 value for Corexit 9500 exposures to Menidia beryllina was 73.1 mg/L (one product was less toxic and seven products were more toxic).     

THE USE OF TOXICITY TESTING IN EFFLUENT REGULATION AND CONTROL: A NEW DIMENSION TO ASSESSMENT AND MANAGEMENT OF WATER QUALITY IN SOUTH AFRICA

Summary

Efficient management tools are continually required to cope with increasing demands placed on the quality and quantity of aquatic resources. Recent developments in environmental monitoring indicate the importance of incorporating biological indicators in assessment programmes. Aquatic toxicology has consequently become an important monitoring and regulatory science. Applications of aquatic toxicity testing include: deriving water quality criteria; toxicological evaluations of whole effluents and receiving waters; and the estimation of ecological risk. Toxicity testing can potentially play a significant role in improving water quality in years to come, especially through its application in effluent regulation. Currently however, few environmental laboratories in South Africa have the required expertise and facilities to carry out a representative range of toxicity tests. Training and funding are required to build the capacity for the necessary developmental research, before toxicity testing can routinely be implemented.

The significant problems we face cannot be solved at the same level of thinking we were at when we created them. Albert Einstein.     

Invited Debate/Commentary: Selenium — A Potential Time Bomb or Just Another Contaminant?

Environmental issues related to selenium are complex and not universally understood. This paper provides detailed information regarding selenium and associated aquatic environmental issues, and then introduces and comments on five debate/commentary papers discussing selenium in the context of the title of this paper. Selenium has a complex and not fully understood biogeochemistry in the aquatic environment as well as an unusual mode of toxicity (acute via water column exposure; chronic via food chain exposure). It has the narrowest range between nutritional requirements and toxicity of any essential element, and chronic toxicity is not readily predictable. Selenium contamination of waters or even of tissues does not necessarily indicate a ticking time bomb; there are no generally accepted or universally accepted threshold values for chronic toxicity. Assessing risk must be done site-specifically in a risk assessment framework, focusing on reproductive effects to sensitive exposed fish and waterfowl and on “worst case” hydrologic units. Unless selenium inputs decrease or site-specific biogeochemistry can be shown not to change, continued biological monitoring and testing are required. Provided the necessary investigative and monitoring studies are done, any potential selenium time bombs can be defused.     

Ecotoxicological assessment of lanthanum with Caenorhabditis elegans in liquid medium

With their widespread applications in industry, agriculture and many other fields, more and more rare earth elements (REEs) are getting into the environment, especially the aquatic systems. Therefore, understanding the aquatic ecotoxicity of REEs has become more and more important. In the present work, Caenorhabditis elegans (C. elegans) was used as a test organism and life-cycle endpoints were chosen along with elemental assay to evaluate the aquatic toxicity of lanthanum (La), a representative of REEs. The results show La3+ had significant adverse effects on the growth and reproduction of worms above a concentration of 10 μmol L?1. The elemental mapping by microbeam synchrotron radiation X-ray fluorescence (μ-SRXRF) illustrated how La treatment disturbed the metals distribution in the whole body of a single tiny nematode at lower levels. Our results suggested that the high-level REEs in some polluted water bodies would lead to an aquatic ecological crisis. The assessment we performed in the present work could be developed as a standardized test design for aquatic toxicological research.     

The Need for Multiple Lines of Evidence for Predicting Site-Specific Ecological Effects

The goal of this paper is to illustrate the value and importance of the “weight of evidence” approach (use of multiple lines of evidence from field and laboratory data) to assess the occurrence or absence of ecological impairment in the aquatic environment. Single species toxicity tests, microcosms, and community metric approaches such as the Index of Biotic Integrity (IBI) are discussed. Single species toxicity tests or other single lines of evidence are valuable first tier assessments that should be used as screening tools to identify potentially toxic conditions in a effluent or the ambient environment but these tests should not be used as the final quantitative indicator of absolute ecological impairment that may result in regulatory action. Both false positive and false negative predictions of ecological effects can occur due to the inherent variability of measurement endpoints such as survival, growth and reproduction used in single species toxicity tests. A comparison of single species ambient toxicity test results with field data showed that false positives are common and likely related to experimental variability or toxicity to selected test species without measureable effects on the ecosystem. Results from microcosm studies have consistently demonstrated that chemical exposures exceeding the acute or chronic toxicity concentrations for highly sensitive species may cause little or no ecologically significant damage to an aquatic ecosystem. Sources of uncertainty identified when extrapolating from single species tests to ecological effects were: variability in individual response to pesticide exposure; variation among species in sensitivity to pesticides; effects of time varying and repeated exposures; and extrapolation from individual to population-level endpoints. Data sets from the Chesapeake Bay area (Maryland) were used to show the importance of using “multiple lines of evidence” when assessing biological impact due to conflicting results reported from ambient water column and sediment toxicity tests and biological indices (benthic and fish IBIs). Results from water column and sediment toxicity tests with multiple species in tidal areas showed that no single species was consistently the most sensitive. There was also a high degree of disagreement between benthic and fish IBI data for the various stations. The lack of agreement for these biological community indices is not surprising due to the differences in exposure among habitats occupied by these different taxonomic assemblages. Data from a fish IBI, benthic IBI and Maryland Physical Habitat Index (MPHI) were compared for approximately 1100 first through third-order Maryland non-tidal streams to show the complexity of data interpretation and the incidence of conflicting lines of evidence. A key finding from this non-tidal data set was the need for using more than one biological indicator to increase the discriminatory power of identifying impaired streams and reduce the possibility of “false negative results”. Based on historical data, temporal variability associated with an IBI in undisturbed areas was reported to be lower than the variability associated with single species toxicity tests.     

The Challenges of Hazard Identification and Classification of Insoluble Metals and Metal Substances for the Aquatic Environment

The OECD is currently harmonizing procedures for aquatic hazard identification of substances. Such a system already exists in Europe where it is recognized that special consideration must be given to sparingly soluble metals and metal compounds (SSMMCs) because standard hazard testing procedures designed for organic chemicals do not accommodate the characteristics of SSMMCs. Current aquatic hazard identification procedures are based on persistence, bioaccumulation, and toxicity (PBT) measurements. Persistence measurements typically used for organic substances (biodegradation) do not apply to metals. Alternative measurements such as complexation and precipitation are more appropriate. Metal bioaccumulation is important in terms of nutritional sufficiency and potential food chain transfer and toxicity. Unlike organic substances, metal bioaccumulation potential cannot be estimated using log octanol-water partition coefficients. Further, bioaccumulation and bioconcentration factors are often inversely related to exposure concentration for most metals and organisms, and hence are not reliable predictors of chronic toxicity or food chain accumulation. Metal toxicity is due predominately to the free metal ion in solution. In order to assess the toxicity of SSMMCs, the rate and extent of transformation to a soluble form must be measured.     

Effects of Chronic Waterborne and Dietary Metal Exposures on Gill Metal-Binding: Implications for the Biotic Ligand Model

The biotic ligand modeling (BLM) approach has gained recent widespread interest among the scientific and regulatory communities because of its potential for developing ambient water quality criteria (AWQC), which are site-specific, and in performing aquatic risk assessment for metals. Currently, BLMs are used for predicting acute toxicity (96?h LC50 for fish) in any defined water chemistry. The conceptual framework of the BLM has a strong physiological basis because it considers that toxicity of metals occurs due to the binding of free metal ions at the physiologically active sites of action (biotic ligand, e.g., fish gill) on the aquatic organism, which can be characterized by conditional binding constants (log K) and densities (B_max). At present, these models assume that only water chemistry variables such as competing cations (e.g., Na⁺, Ca²⁺, Mg²⁺, and H⁺), inorganic ligands (e.g., hydroxides, chlorides, carbonates), and organic ligands (dissolved organic matter) can influence the bioavailability of free metal ions and thereby the acute toxicity of metals. Current BLMs do not consider the effects of chronic history of the fish in modifying gill-metal binding characteristics and acute toxicity. Here, for Cu, Cd, and Zn, we review a number of recent studies on the rainbow trout that describe significant modifying effects of chronic acclimation to waterborne factors (hardness and chronic metal exposure) and dietary composition (metal and essential ion content) on gill metalbinding characteristics (on both log K and B_max) and on acute toxicity. We conclude that the properties of gill-metal interaction and toxicological sensitivity appear to be dynamic rather than fixed, with important implications for further development of both acute and chronic BLMs. Now that the initial framework of the BLM has been established, future research needs a more integrative approach with additional emphasis on the dynamic properties of the biotic ligand to make it a successful tool for ecological risk assessment of metals in the natural environment.     

Separation and aquatic toxicity of enantiomers of the organophosphorus insecticide trichloronate

Many of the organophosphorus pesticides (OPs) currently used are chiral and therefore consist of mixture of enantiomers. Despite the fact that the biological processes of chiral pesticides are enantioselective, the acute aquatic toxicity of chiral OPs with respect to enantioselectivity has so far received limited research. In this study, the enantiomeric separation and acute aquatic toxicity of trichloronate were investigated. Baseline enantioseparation of trichloronate was successfully achieved using high-performance liquid chromatography on a Chiralcel OJ column, with a mobile phase of n-hexane/n-heptane/ethanol (90/5/5, v/v/v) at the flow rate of 1.0 ml min(-1) and room temperature. The resolved enantiomers were characterized for their optical rotation and by gas chromatography coupled with mass spectrometry. Significant differences were found between the enantiomers in acute aquatic toxicity to Ceriodaphnia dubia and Daphnia magna. The (-)-trichloronate was 8-11 times more toxic to the test organisms than its (+)-form, while the racemate showed intermediate toxicity. These results suggest that assessment of the environmental safety of chiral OPs should take stereospecificity into consideration.