An in situ toxicity identification evaluation method Part II: Field validation

When sediments are found to be toxic usually there is a mixture of chemicals present. Often it is important to establish which chemicals contribute to the toxicity. Establishing causality can be difficult and often requires fractionation with subsequent toxicity testing. The sample collection and manipulation process can alter chemical bioavailability and toxicity. An in situ toxicity identification evaluation (iTIE) chamber is described that was placed in sediments and fractionated pore-water chemicals into nonpolar chemicals, metals, and ammonia-type groups. This method was field tested and compared to the laboratory-based, U.S. Environmental Protection Agency (U.S. EPA) toxicity identification evaluation (TIE) method. Field studies were performed at three sites contaminated primarily with polycyclic aromatic hydrocarbons (PAHs) (Little Scioto River, OH, USA), polychlorinated biphenyls (PCBs) (Dicks Creek, OH, USA), and chlorobenzenes (Sebasticook River, ME, USA). Both the iTIE and the U.S. EPA TIE methods used Daphnia magna in 24-h exposures. Although the iTIE and TIE were conducted on sediments from the same location, there was significantly more toxicity observed in the iTIE testing. The dominant chemical classes were separated by the iTIE method and revealed which fractions contributed to toxicity. The loss of toxicity in the TIE approach did not allow for subsequent fractionation and stressor identification. Advantages of the iTIE over the TIE method were greater sensitivity and ability to detect causative toxic chemical fractions; lack of sediment collection and subsequent manipulation; and, thus, reduction in potential artifacts, more realistic exposure with slow, continual pore-water renewal in situ, ability to evaluate pore waters in sandy or rocky substrates where pore waters are difficult to collect, and a quicker phase I evaluation. Limitations of the iTIE method as compared to the TIE methods were extensive pretest assembly process, fewer phase I fractionation possibilities, and restriction to shallow waters. The results of these studies suggest that the iTIE method provides a more accurate and sensitive evaluation of pore water toxicity than the laboratory TIE method.     

Importance of equilibration time in the partitioning and toxicity of zinc in spiked sediment bioassays

The influences of spiked Zn concentrations (1-40 micromol/g) and equilibration time (approximately 95 d) on the partitioning of Zn between pore water (PW) and sediment were evaluated with estuarine sediments containing two levels (5 and 15 micromol/g) of acid volatile sulfides (AVS). Their influence on Zn bioavailability was also evaluated by a parallel, 10-d amphipod (Leptocheirus plumulosus) mortality test at 5, 20, and 85 d of equilibration. During the equilibration, AVS increased (up to twofold) with spiked Zn concentration ([Zn]), whereas Zn-simultaneously extracted metals ([SEM]; Zn with AVS) remained relatively constant. Concentrations of Zn in PW decreased most rapidly during the initial 30 d and by 11- to 23-fold during the whole 95-d equilibration period. The apparent partitioning coefficient (Kpw, ratio of [Zn] in SEM to PW) increased by 10- to 20-fold with time and decreased with spiked [Zn] in sediments. The decrease of PW [Zn] could be explained by a combination of changes in AVS and redistribution of Zn into more insoluble phases as the sediment aged. Amphipod mortality decreased significantly with the equilibration time, consistent with decrease in dissolved [Zn]. The median lethal concentration (LC50) value (33 microM) in the second bioassay, conducted after 20 d of equilibration, was twofold the LC50 in the initial bioassay at 5 d of equilibration, probably because of the change of dissolved Zn speciation. Sediment bioassay protocols employing a short equilibration time and high spiked metal concentrations could accentuate partitioning of metals to the dissolved phase and shift the pathway for metal exposure toward the dissolved phase.     

Modeling zinc toxicity for terrestrial invertebrates

Acute and chronic ecotoxicity tests with zinc were performed with the earthworm Eisenia fetida, the potworm Enchytraeus albidus, and the springtail Folsomia candida. To assess the influence of the soil type on zinc toxicity for these soil invertebrates, these tests were carried out in a standard artificial soil, a sandy and a loamy field soil. Based on the results of this experimental work and data taken from literature, models were developed relating the ecotoxicity of zinc to the most important parameters controlling bioavailability: pH and cation exchange capacity. Models were developed for E. fetida and F. candida using the regression technique partial least squares projection to latent structures (PLS). Acute as well as chronic toxicity data of both organisms could be normalized on the basis of the pH and the cation exchange capacity of the test soils. For other terrestrial invertebrates, not enough data were available to develop reliable models.     

Alterations in zinc absorption and salivary sediment zinc after a lacto-ovo-vegetarian diet

The effect of a lacto-ovo-vegetarian diet on plasma zinc tolerance tests and plasma and saliva zinc levels was measured in 12 nonvegetarian women. A diet meeting the Recommended Dietary Allowances for all nutrients, including zinc, was fed to the subjects for 22 days. Initial zinc status of subjects was determined by zinc analysis of their diet, hair, plasma, and saliva. Plasma response to an oral load of 50 mg Zn was determined in five subjects before and after the dietary period. Zinc levels of salivary sediment, which consisted primarily of epithelial cells, significantly decreased from initial values of 128 to final levels, of 94 microgram/g. No significant differences were found in zinc levels of plasma or whole mixed saliva. Plasma response to initial zinc tolerance tests were inversely correlated (P < 0.05) to dietary protein levels. Significantly increased plasma zinc uptake and areas under zinc tolerance curves were found after consumption of vegetarian diets compared to diets containing meats. The increased plasma response to a zinc load and decrease in salivary sediment zinc after a vegetarian diet indicate that this diet adversely affects zinc status.     

Formulated sediment as a reference and dilution sediment in definitive toxicity tests

To accurately determine the relative potency of contaminated sediments that exhibit toxicity in screening tests, definitive toxicity tests are conducted by diluting test sediment with a nontoxic reference sediment of similar characteristics. To demonstrate the usefulness of formulated sediment as a reference and dilution sediment, the relative potency of a copper-contaminated sediment was assessed by diluting with a formulated sediment. Toxicity of sediment-bound copper was assessed by monitoring the survival of Ceriodaphnia dubia Richard, Daphnia magna Straus, Hyalella azteca Saussure, Chironomus tentans Fabricius, and Pimephales promelas Rafinesque. Organisms were exposed in static systems for 10 d using test sediment dilutions that produced mortality in range-finding tests. Formulated sediment served as a suitable control sediment, with organism survival ranging from 85–100%. Formulated sediment was prepared and matched ten of eleven characteristics of the field-collected test sediment. When used to dilute the copper-contaminated sediment, formulated sediment resulted in decreased concentrations of copper in sediment, pore water, and overlying water with concomitant increases in test dilution. Thus, formulated sediment served as a suitable reference and dilution sediment in this study. Evidence indicates that formulated sediments could be used in this capacity when suitable natural reference sediments are otherwise unavailable.     

Chemical availability and sediment toxicity of pyrethroid insecticides to Hyalella azteca: application to field sediment with unexpectedly low toxicity

Tenax extraction is a simple, inexpensive approach to estimate the bioavailability of hydrophobic organic contaminants from sediment. In the present study, a single-point Tenax extraction was evaluated regarding its correlation with the acute toxicity to Hyalella azteca using field-collected sediments in California, USA. Pyrethroids were believed to be the primary contributor to the observed toxicity, and a significant correlation existed between the expected toxicity (given pyrethroid concentrations) and the mortality at most sampling sites. A small subset of sites, however, showed unexpectedly low toxicity to H. azteca despite high concentrations of pyrethroids. These samples were evaluated by Tenax extraction with the expectation that this procedure, which qualifies bioavailable instead of total pyrethroid concentration in sediment, would better explain the anomalously low toxicity. The term bioavailable toxic unit was proposed to link sediment toxicity with chemical availability, and the toxicity in the 17 selected sediments was better explained using Tenax extraction. The r2 value of the regression between sediment toxicity and toxic unit for the 17 sediments increased from 0.24 to 0.60 when the Tenax-extractable concentration was used in place of the total concentration. Results also showed that adsorption to sand particles might play a controlling role in pyrethroid bioavailability and, in turn, sediment toxicity to benthic invertebrates.     

A field validation of two sediment-amphipod toxicity tests

A field validation study of two sediment-amphipod toxicity tests was conducted using sediment samples collected subtidally in the vicinity of a polycyclic aromatic hydrocarbon (PAH)-contaminated Superfund site in Elliott Bay (WA, USA). Sediment samples were collected at 30 stations with a 0.1 m2 grab from which subsamples were taken for sediment toxicity testing and geochemical and macrofaunal analyses. Standard 10-d sediment-amphipod toxicity tests were conducted with Rhepoxynius abronius and Leptocheiros plumulosus. Sediments were analyzed for 33 PAHs, pentachlorophenol, polychlorinated biphenyls, acid-volatile sulfide, simultaneously extracted metals (Cd, Cu, Zn, Pb, Ni), total organic carbon, and grain size. Sediment temperature, oxygen-reduction potential, water depth, and interstitial water salinity were also measured. Polycyclic aromatic hydrocarbons, quantified as total PAH toxic units (TU(PAH)), were confirmed to be an important common causal agent of the changes in the two toxicity test (% survival R. abronius, % survival L. plumulosus) and five macrofaunal community (number of species, S; numerical abundance, A: total biomass, B: Swartz's dominance index, SDI; Brillouin's index, H) endpoints. Two other macrofaunal community metrics (the complement of Simpson's index, 1 - SI, and McIntosh's index, MI) were less sensitive to TU(PAH) than the two toxicity test endpoints. The sensitivities of R. abronius and L. plumulosus to TU(PAH) were statistically indistinguishable. Field validations were conducted by testing the association between or among each toxicity test endpoint, each of seven macrofaunal community metrics (S, A, B, SDI, H, 1 - SI, MI), and TU(PAH) by (1) Spearman's coefficient of rank correlation, (2) Kendall's coefficient of concordance, (3) G tests of independence, and (4) regression analysis. Some field validations based on multivariable tests of association (e.g., points 2 and 3) among toxicity test, field, and stressor endpoints produced false positive results. Both toxicity test endpoints were validated as indicators of changes in S, A, SDI, and H by all the methods tested. The resolution power of the relationships between the laboratory toxicity test and macrofaunal field endpoints was low (< or = three classes) but sufficient to discriminate ecologically important effects. We conclude that standard sediment-amphipod toxicity tests are ecologically relevant and that, under the proper conditions, their results can be used for lab-to-field extrapolation.     

锌镉毒性研究进展

目的:总结近年来国内外对于锌镉毒性的研究进展。方法:搜集、分析国内外相关文献。结果:动物实验研究表明:镉对鼠类的生殖系统、骨骼发育以及听力系统均有毒作用,镉可引起鱼类卵壳破裂,锌能拮抗镉对动物的毒性作用。人体研究表明:锌不仅能提高人体免疫力而且能拮抗镉对人体的毒性作用,镉对人体的健康效应主要表现在对人体呼吸、泌尿、消化、运动、生殖系统等方面的毒性作用。结论:锌镉相互拮抗,锌可预防和减轻镉中毒的危害。     

锌对大鼠生殖毒性的影响

为观察锌摄入对大鼠生殖功能的影响。结果显示 ,连续 60天给予低剂量 12mg kg、中剂量 12 0mg kg的锌可使雄性大鼠精子的数目和精子的活动度升高 ,大鼠生殖功能提高 ,高剂量 2 40mg kg的锌可造成生殖系统损伤 ,致使生殖功能的降低 ,但未见影响子代的生长和发育。提示高剂量的锌对雄性大鼠生殖系统有一定的损伤     

Recommendations for the assessment of TNT toxicity in sediment

Previous investigations of the ecotoxicity of TNT in spiked sediments noted the rapid degradation and disappearance of the toxicant, yet little is understood regarding the effects of this process on toxicity and subsequent derivation of toxicity reference values. We conducted environmental fate studies and 28-d sediment toxicity tests with benthic oligochaete worms (Tubifex tubifex) with sediments spiked at three different TNT concentrations (440, 1,409, and 4,403 nmol/g dry wt) aged for 1, 8, and 29 d. Because of rapid degradation of TNT, disappearance of degradation products, and partitioning to overlying water, only 25 to 40% of the added nitroaromatic mass balance was associated with sediment immediately after spiking. Lethal toxicity decreased with aging time and was best described by measured sediment nitroaromatic concentrations (sum of TNT and degradation products) at the beginning of exposure, with a median lethal concentration of nitroaromatic compounds of 184 nmol/g dry weight. To accurately describe the ephemeral exposure doses of TNT and its degradation products during toxicity tests with spiked sediments, we suggest that sediments should be aged at least 8 to 14 d after spiking, exposure should be based on measured sediment concentrations or chemical measures of availability, exchange of overlying water should be avoided or minimized, and short-term toxicity tests should be considered.     

Comparative sediment quality guideline performance for predicting sediment toxicity in southern California, USA

Several types of sediment quality guidelines (SQGs) are used by multiple agencies in southern California (USA) to interpret sediment chemistry data, yet little information is available to identify the best approaches to use. The objective of this study was to evaluate the predictive ability of five SQGs to predict the presence and absence of sediment toxicity in coastal southern California: the effects range-median quotient (ERMq), consensus moderate effect concentration (consensus MEC), mean sediment quality guideline quotient (SQGQ1), apparent effects threshold (AET), and equilibrium partitioning (EqP) for organics. Large differences in predictive ability among the SQGs were obtained when each approach was applied to the same southern California data set. Sediment quality guidelines that performed well in identifying nontoxic samples were not necessarily the best predictors of toxicity. In general, the mean ERMq, SQGQ1q, and consensus MECq approaches had a better overall predictive ability than the AET and EqP for organics approaches. In addition to evaluating the predictive ability of SQGs addressing chemical mixtures, the effect of an individual SQG value (DDT) was also evaluated for the mean ERMq with and without DDT. The mean ERMq without DDT had a better ability to predict toxic samples than the mean ERMq with DDT. Similarities in discriminatory ability between different approaches, variations in accuracy among SQG values for some chemicals, and the presence of complex mixtures of contaminants in most samples underscore the need to apply SQGs in combination, such as the mean quotient. Management objectives and SQG predictive ability using regional data should be determined beforehand so that the most appropriate SQG approach and critical values can be identified for specific applications.     

Inhibition of aquatic toxicity of pyrethroid insecticides by suspended sediment

The use of pyrethroid insecticides is increasing in both agricultural and urban environments. Although pyrethroids display very high acute toxicities to water column organisms in laboratory tests, environmental water samples typically contain suspended sediment (SS) that can reduce the freely dissolved concentration of pyrethroids, hence their bioavailability. Consequently, phase distribution could play an important role in pyrethroid aquatic toxicology. In this study, we evaluated the effect of SS on the acute toxicity of four widely used pyrethroid insecticides to Ceriodaphnia dubia. In all assays, median lethal concentrations (LC50s) consistently increased with increasing SS, demonstrating the pronounced inhibitory effects of SS on pyrethroid toxicity. The LC50s in the 200 mg/L SS solutions were 2.5 to 13 times greater than those measured in sediment-free controls. Solid-phase microextraction (SPME) was used to determine the apparent distribution coefficient Kd for the pyrethroids in the water samples. Under the assumption that only the freely dissolved fraction is bioavailable, the measured Kd was used to predict C. dubia LC50s in the water samples. The predicted LC50s were within a factor of two of the measured values for 95% of the treatments. Results from this study suggest that the inhibitory effect of SS can be highly significant and must be considered in estimating exposures to pyrethroids in aquatic systems. The SPME methodology could be used effectively to measure bioavailable concentration and to predict the actual ecotoxicologic effects of pyrethroids.     

铅与锌作用的研究

目的:探讨铅与锌对机体的单一、联合作用。方法:收集、分析国内、外关于铅与锌作用的最新文献。结果:铅锌对机体的单独作用:铅元素对机体的影响主要累及造血、消化等功能,损害神经、肝脏、肾脏及心血管系统;锌元素参与体内的糖、脂类和蛋白质三大物质的代谢,是机体正常生长、蛋白质合成、生物膜稳定及若干金属酶发挥功能所必需的微量元素。生活中摄取锌元素时一般不会发生锌中毒,但是大剂量服用含锌制剂以致超出机体代谢的调节能力时会对人体产生损伤。铅、锌的联合作用的研究结果表明:铅拮抗机体内锌代谢作用,锌对机体内铅毒性具有保护作用。结论:铅和锌之间存在相互拮抗作用,其他元素比如铜也对锌的代谢产生拮抗;在对抗铅中毒时,某些微量元素比如维生素C、钙等也可发挥一定的作用。     

Solid-phase sediment toxicity identification evaluation in an agricultural stream

The lower Santa Maria River watershed provides important aquatic habitat on the central California coast and is influenced heavily by agricultural runoff. As part of a recently completed water quality assessment, we conducted a series of water column and sediment toxicity tests throughout this watershed. Sediment from Orcutt Creek, a tributary that drains agricultural land, consistently was toxic to the amphipod Hyalella azteca, which is a resident genus in this river. Toxicity identification evaluations (TIEs) were conducted to determine cause(s) of toxicity. We observed no toxicity in sediment interstitial water even though concentrations of chlorpyrifos exceeded published aqueous toxicity thresholds for H. azteca. In contrast to interstitial water, bulk sediment was toxic to H. azteca. In bulk-phase sediment TIEs, the addition of 20% (by volume) coconut charcoal increased survival by 41%, implicating organic chemical(s). Addition of 5% (by volume) of the carbonaceous resin Ambersorb 563 increased survival by 88%, again suggesting toxicity due to organic chemicals. Toxicity was confirmed by isolating Ambersorb from the sediment, eluting the resin with methanol, and observing significant toxicity in control water spiked with the methanol eluate. A carboxylesterase enzyme that hydrolyzes synthetic pyrethroids was added to overlying water, and this significantly reduced toxicity to amphipods. Although the pesticides chlorpyrifos, DDT, permethrin, esfenvalerate, and fenvalerate were detected in this sediment, and their concentrations were below published toxicity thresholds for H. azteca, additivity or synergism may have occurred. The weight-of-evidence suggests toxicity of this sediment was caused by an organic contaminant, most likely a synthetic pyrethroid.     

Effects of temperature and oxygen concentration in sediment toxicity testing

Joint effects of temperature and oxygen concentrations for the results of sediment toxicity tests were studied at 10 and 20 °C with 40% and 80% dissolved oxygen (DO) saturation. Growth, feeding rate, and reproduction of Lumbriculus variegatus (Oligochaete) and growth, emergence, and survival of Chironomus riparius (Diptera) were tested in a polluted and in a reference sediment. Both the feeding of L. variegatus and the emergence of C. riparius were significantly retarded at low temperature. Additionally, differences in the sex ratio of the emerged adults of C. riparius were observed. The oxygen concentration alone did not have any significant effect on the endpoints, but significant combined effects of polluted sediment and low DO were observed on the biomass of L. variegatus. The standard sediment toxicity tests might offer only limited data for risk assessment of contaminated sediments at sites where the actual conditions largely differ from the laboratory conditions.     

Predicting sediment metal toxicity using a sediment biotic ligand model: methodology and initial application

An extension of the simultaneously extracted metals/acid-volatile sulfide (SEM/AVS) procedure is presented that predicts the acute and chronic sediment metals effects concentrations. A biotic ligand model (BLM) and a pore water-sediment partitioning model are used to predict the sediment concentration that is in equilibrium with the biotic ligand effects concentration. This initial application considers only partitioning to sediment particulate organic carbon. This procedure bypasses the need to compute the details of the pore-water chemistry. Remarkably, the median lethal concentration on a sediment organic carbon (OC)-normalized basis, SEM*(x,OC), is essentially unchanged over a wide range of concentrations of pore-water hardness, salinity, dissolved organic carbon, and any other complexing or competing ligands. Only the pore-water pH is important. Both acute and chronic exposures in fresh- and saltwater sediments are compared to predictions for cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) based on the Daphnia magna BLM. The SEM*(x,OC) concentrations are similar for all the metals except cadmium. For pH = 8, the approximate values (micromol/gOC) are Cd-SEM*(xOC) approximately equal to 100, Cu-SEM*(x,OC) approximately equal to 900, Ni-SEMoc approximately equal to 1,100, Zn-SEM*(x,OC) approximately equal to 1,400, and Pb-SEM*(x,OC) approximately equal to 2,700. This similarity is the explanation for an empirically observed dose-response relationship between SEM and acute and chronic effects concentrations that had been observed previously. This initial application clearly demonstrates that BLMs can be used to predict toxic sediment concentrations without modeling the pore-water chemistry.     

The effects of storage temperature and time on sediment toxicity

The toxicity of an estuarine sediment stored at different temperatures (–22°C, 4°C, and 25°C) was monitored over time (at 0, 2, 4, 7, and 20 weeks) by conducting 96 h suspended particulate phase (SPP) tests with 24- to 48-h-old Mysidopsis bahia. Toxicity generally increased with time for sediments stored at 4°C and –22°C. For both temperature treatments, survival was reduced from 40% at week 0 to <10% at week 12. Survival at 25°C was much more variable, fluctuating between 10% and 90% during the experiment. Reference toxicant tests with sodium dodecyl sulfate (SDS) were conducted throughout the sediment storage experiment. Relative sensitivity to SDS was similar at all time periods except for week 20 where decreased sensitivity was observed. This decreased sensitivity to the reference toxicant corresponded to a significant and uniform increase in survival to all stored sediment samples.     

Comparative toxicity of cadmium, zinc, and mixtures of cadmium and zinc to daphnids

Investigations were conducted to determine acute (48-h) effects of cadmium and zinc presented individually and in combination on Ceriodaphnia dubia, Daphnia magna, Daphnia ambigua, and Daphnia pulex. Toxicity tests were conducted with single metals to determine lethal effects concentrations (lethal concentrations predicted for a given percent [x] of a population, LCx value). These were used to derive metal combinations that spanned a range of effects and included mixtures of LC15, LC50, and LC85 values calculated for each metal and species. In single-metal tests, 48-h LC50 values ranged from 0.09 to 0.9 micromol/L and 4 to 12.54 micromol/L for cadmium and zinc, respectively. For each metal, D. magna was most tolerant and showed a different pattern of response from all others as determined by slope of concentration-response curves. In the combined metal treatments, all daphnids showed a similar pattern of response when LC15 concentrations were combined. This trend continued with few exceptions when LC15 concentrations of cadmium were combined with LC50 or LC85 values for zinc. However, when this treatment was reversed (LC15, zinc + LC50 or LC85, cadmium), responses of all species except D. magna indicated less-than-additive effects. For C. dubia, a near complete reduction in toxicity was observed when the LC15 for zinc was combined with LC85 for cadmium. Multimetal tests with D. magna did not differ from additive. Collectively, these studies suggest that D. magna may not be representative of other cladocerans.