Using solid-phase microextraction during ultrasound reveals higher aqueous PAHs release from contaminated sediment.

Ultrasound (US) releases polycyclic aromatic hydrocarbons (PAHs) from contaminated creosote sediments and degrades PAHs in aqueous solution. However, it is unclear how much PAHs release occurs during active US compared to after US is stopped. In this study, solid-phase microextraction (SPME) was used to determine aqueous PAH concentrations desorbed from Little Scioto River creosote contaminated sediment during exposure to 20 kHz ultrasound (US) at a power of 430 W L-1. First, SPME fiber-water partition coefficients,KSPME, were experimentally determined and shown to be comparable with previous studies. Next, PAH concentrations released into aqueous solution were determined by sequentially exposing fresh, conditioned SPME fibers in a reactor containing the contaminated sediment and DI for 10 min periods. Three consecutive 10 min periods each were measured during US and after US. Compared to mixing only, PAHs desorbed during ultrasound was significantly higher. In addition, for phenanthrene, anthracene, and fluoranthene, US showed significantly higher aqueous concentrations during US compared with after US. For these less soluble PAHs, desorption into the aqueous phase reaches and surpasses expected equilibrium aqueous concentrations. However, when US is ceased, PAHs appear to resorb onto sediment resulting in the lower concentrations measured in these PAH compounds after US that are similar to expected equilibrium aqueous concentrations. Typical analytical extraction methods for determining the effects of US require stopping treatment and may underestimate the potential US has for release of contaminants from sediment during US. Using SPME during US treatment reveals that the concentration of PAHs during US may surpass the expected equilibrium aqueous concentration of some PAHs congeners. To our knowledge, this higher concentration observed during US compared to after US has not been shown previously.

Toward Sustainable Environmental Quality: Priority Research Questions for North America.

Anticipating, identifying, and prioritizing strategic needs represent essential activities by research organizations. Decided benefits emerge when these pursuits engage globally important environment and health goals, including the United Nations Sustainable Development Goals. To this end, horizon scanning efforts can facilitate identification of specific research needs to address grand challenges. We report and discuss 40 priority research questions following engagement of scientists and engineers in North America. These timely questions identify the importance of stimulating innovation and developing new methods, tools, and concepts in environmental chemistry and toxicology to improve assessment and management of chemical contaminants and other diverse environmental stressors. Grand challenges to achieving sustainable management of the environment are becoming increasingly complex and structured by global megatrends, which collectively challenge existing sustainable environmental quality efforts. Transdisciplinary, systems-based approaches will be required to define and avoid adverse biological effects across temporal and spatial gradients. Similarly, coordinated research activities among organizations within and among countries are necessary to address the priority research needs reported here. Acquiring answers to these 40 research questions will not be trivial, but doing so promises to advance sustainable environmental quality in the 21st century. Environ Toxicol Chem 2019;38:1606-1624. © 2019 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

Effects of Soil Properties on the Toxicity and Bioaccumulation of Lead in Soil Invertebrates.

The present study examined the effects of soil physical and chemical properties on the toxicity of lead (Pb) to earthworms (Eisenia fetida) and collembolans (Folsomia candida), and on bioaccumulation of Pb by earthworms, in soils amended with Pb salts. Toxicity tests were conducted in 7 soils varying in soil properties (pH 4.7-7.4, effective cation exchange capacity [eCEC] 4-42 cmolc /kg, organic carbon 10-50 g C/kg) that were leached and pH corrected after spiking with PbCl2 . The median effect concentrations (EC50s) based on total soil Pb concentrations ranged from 35 to 5080 mg Pb/kg for earthworms and 389 to >7190 mg/kg for Collembola. Significant positive correlations were observed between log (EC50) for earthworm reproduction and log (eCEC, total C, exchangeable Ca and Mg, or clay content), but no significant correlations were observed between Pb toxicity to Collembola and soil properties. Expressing Pb dose as either the free ion (Pb2+ ) activity in porewater or as the measured dissolved porewater concentration of Pb did not explain differences in toxicity among soils. The bioaccumulation factors (BAFs) for Pb in earthworms ranged up to >10-fold across 6 soil treatments, with a median of 0.16, and the BAF was significantly correlated with eCEC (p = 0.038, r = -0.84), but not with any other soil properties. Soil properties related to eCEC (total C, exchangeable Ca and Mg, clay content) had a significant effect on Pb toxicity and bioaccumulation in earthworms, but no relationship was found for Collembola. As a major soil property affecting the bioavailability of Pb, CEC should be incorporated into any soil hazard assessment of Pb as a modifying factor of toxicity and bioaccumulation for earthworms. Environ Toxicol Chem 2019;38:1486-1494. © 2019 SETAC.

Ecological impacts of fluridone and copper sulphate in catfish aquaculture ponds.

Fluridone and copper sulphate are often used for controlling macrophytes and algae in aquaculture ponds. The present study examined the ecological effects of these chemicals on macrophyte, phytoplankton, and zooplankton biomass; plankton community structure; water quality parameters; and fish survival and yield in catfish culture ponds using a randomized complete block design. The estimated half-life of fluridone in the individual ponds ranged from 1.6 d to 10.8 d. Free copper ion activity in ponds treated with copper sulphate was dynamic, ranging from pCu of 7.7 to 8.9 after each application and decreasing to approximately 12 (1 × 10(-12) M) within 1 wk after each application, approaching observed values in control ponds (pCu = 12.3-13.4). No difference in macrophyte biomass was observed among treatments. Fluridone and copper treatments elicited different responses within the phytoplankton community. Copper treatments reduced Cyanophyta biomass but increased biomass of more tolerant taxa among the Chlorophyta and Chrysophyta. Fluridone treatments reduced total phytoplankton biomass including Cyanophyta and increased the sensitivity of Chlorophyta and Chrysophyta to copper. Copper also affected zooplankton community composition as a result of direct toxic effects on sensitive zooplankton taxa (e.g., Cladocera), whereas Copepoda biomass in copper-treated ponds exceeded that in controls. Catfish survival and yield were not significantly different among treatments. The results of the present study suggest that fluridone and copper interact at realistic application rates, increasing the ability to control algae compared with treatments where they are applied alone.

Differential acute toxicity of tetrachlorobenzene isomers to oligochaetes in soil and water: application of the critical body residue concept.

The acute, lethal potency of the 1,2,3,4-, 1,2,4,5- and 1,2,3,5-tetrachlorobenzene isomers was compared in the terrestrial and aquatic oligochaetes Eisenia andrei and Tubifex tubifex. 1,2,4,5-TeCB was neither lethal, nor produced any perceptible adverse effects, at lipid normalized concentrations predicted to be lethal according to the well-established critical body residue concept. If a narcotic is defined as a substance capable of inducing narcosis, rather than a substance displaying certain physical or chemical properties (e.g., log K(ow)), then we do not believe these findings challenge the critical body residue because by the former definition, 1,2,4,5-tetrachlorobenzene is not a narcotic.

Application of the tissue residue approach in ecological risk assessment.

The objective of this work is to present a critical review of the application of the tissue residue approach (TRA) in ecological risk and/or impact assessment (ERA) of chemical stressors and environmental criteria development. A secondary goal is to develop a framework for integrating the TRA into ecological assessments along with traditional, exposure concentration-based assessment approaches. Although widely recognized for its toxicological appeal, the utility of the TRA in specific applications will depend on numerous factors, such as chemical properties, exposure characteristics, assessment type, availability of tissue residue-response data, and ability to quantify chemical exposure. Therefore, the decision to use the TRA should include an evaluation of the relative strengths, limitations, and uncertainties among exposure and residue-based methods for characterizing toxicological effects. Furthermore, rather than supplanting exposure concentration-based toxicity assessments, the TRA can be highly effective for evaluating and reducing uncertainty when used in a complementary manner (e.g., when evaluating multiple lines of evidence in field studies). To address limitations with the available tissue residue-response data, approaches for extrapolating residue-based toxicity data across species, tissues, and exposure durations are discussed. Some of these approaches rely on predicted residue-response relationships or toxicological models that have an implicit residue-response basis (e.g., biotic ligand model). Because risk to an organism is a function of both its exposure potential and inherent sensitivity (i.e., on a residue basis), bioaccumulation models will be required not only for translating tissue residue criteria into corresponding water and sediment criteria, but also for defining the most vulnerable species in an assemblage (i.e., highly exposed and highly sensitive species). Application of the TRA in ecological assessments and criteria development are summarized for bioaccumulative organic chemicals, TBT, and in situ bioassays using bivalve molluscs.

Uptake kinetics and subcellular compartmentalization of cadmium in acclimated and unacclimated earthworms (Eisenia andrei).

Acclimation to cadmium (Cd) levels exceeding background concentrations may influence the ability of earthworms to accumulate Cd with minimum adverse effects. In the present study, earthworms (Eisenia andrei) were acclimated by exposure to 20 mg/kg Cd (dry wt) in Webster soil for 28 d. A 224-d bioaccumulation test was subsequently conducted with both acclimated and unacclimated worms exposed in Webster soils spiked with 20 mg/kg and 100 mg/kg Cd (dry wt). Uptake kinetics and subcellular compartmentalization of Cd were examined. Results suggest that acclimated earthworms accumulated more Cd and required a longer time to reach steady state than unacclimated worms. Most of the Cd was present in the metallothionein (MT) fraction. Cadmium in the MT fraction increased approximately linearly with time and required a relatively longer time to reach steady state than Cd in cell debris and granule fractions, which quickly reached steady state. Cadmium in the cell debris fraction is considered potentially toxic, but low steady state concentrations observed in the present study would not suggest the potential for adverse effects. Future use of earthworms in ecological risk assessment should take into consideration pre-exposure histories of the test organisms. A prolonged test period may be required for a comprehensive understanding of Cd uptake kinetics and compartmentalization.

Determining exposure dose in soil: the effect of modifying factors on chlorinated benzene toxicity to earthworms.

This study describes the comparison of multiple approaches for estimating the median lethal concentration of selected chlorinated benzenes (CBs) from an homologous series yielding acute toxicity to the earthworm Eisenia andrei in Webster soil. The coefficients of variation were significantly lower for solid-phase microextraction (SPME), tissue residue, and hexane-extractable based CB exposure estimates compared to nominal CB exposure estimates. The range of CB exposure estimates based on SPME, tissue residue, or nominal was narrower than lethal concentration exposure estimates based on hexane-extractable CBs. Despite the insignificant difference between the coefficients of variation for SPME and hexane-extractable based measures of CB exposure, the results of this study suggest that the use of SPME based estimates of exposure may improve the accuracy of ecological risk assessment when used an alternative to hexane-extractable (total soil CBs) due to a narrower range of medial lethal concentrations when comparing equipotent compounds.

Evaluating the contribution of soil properties to modifying lead phytoavailability and phytotoxicity.

Soil properties affect Pb bioavailability to human and ecological receptors and should be considered during ecological risk assessment of contaminated soil. We used path analysis (PA) to determine the relative contribution of soil properties (pH, organic C [OC], amorphous Fe and Al oxides [FEAL], and cation-exchange capacity [CEC]) in modifying Pb bioavailability. The response of biological endpoints (bioaccumulation and dry matter growth [DMG]) of lettuce (Lactuca sativa) grown on 21 Pb-spiked (2,000 mg/kg) soils were determined. Lettuce tissue Pb ranged from 3.22 to 233 mg/kg, and relative DMG ranged from 2.5 to 88.5% of their respective controls. Simple correlation showed strong relationships between CEC and OC (p < 0.01) and weaker relationships between pH and FEAL (p < 0.05) and Pb bioaccumulation. Results of PA suggest that soil pH increased the negative surface charge of organic matter and clay, thereby increasing CEC and decreasing Pb bioaccumulation. Also, the direct effect of OC on tissue Pb can be attributed to formation of surface Pb complexes by organic matter functional group ligands. Increased OC and/or CEC reduced Pb solubility and bioavailability in the 21 soils in the present study. The relative importance of soil properties likely will vary between studies employing different soils. Soil properties should be considered during the ecological risk assessment of metal in contaminated soils. Path analysis is useful for ecological studies involving soils with a wide range of physicochemical properties and can assist in site risk assessment of metals and remediation decisions on contaminated sites.

Effect of soil properties on lead bioavailability and toxicity to earthworms.

Soil properties are important factors modifying metal bioavailability to ecological receptors. Twenty-one soils with a wide range of soil properties (USA; http://soils.usda.gov/technical/classification/taxonomy/) were amended with a single concentration of Pb (2,000 mg/kg) to determine the effects of soil properties on Pb bioavailability and toxicity to earthworms. Earthworm mortality ranged from 0 to 100% acute mortality following exposure to the same total concentration of Pb (2,000 mg/kg) in amended field soils. Internal Pb concentrations in earthworms ranged from 28.7 to 782 mg/kg, with a mean of 271 mg/kg. Path analysis was used to partition correlations in an attempt to discern the relative contribution of each soil property. Results of path analysis indicated that pH was the most important soil property affecting earthworm mortality (p < 0.01) and internal Pb (p < 0.05). Soil pH was related inversely to mortality and internal Pb, soil solution Pb, and Pb bioavailability. The most important soil property modifying reproduction was amorphous iron and aluminum oxides (FEAL). Because FEAL is rich in pH-dependent cation-exchange sites, several soil properties, including pH, FEAL, and cation-exchange capacity, have a causal effect on Pb adsorption and soluble Pb. Path analysis is useful for assessing contaminated soils with a wide range of soil properties and can assist in ecological risk assessment and remediation decisions for contaminated sites. Soil properties are important factors modifying metal bioavailability and toxicity and should be considered during the ecological risk assessment of metals in contaminated soils.

Biological significance of metals partitioned to subcellular fractions within earthworms (Aporrectodea caliginosa).

Metal ions in excess of metabolic requirements are potentially toxic and must be removed from the vicinity of important biological molecules to protect organisms from adverse effects. Correspondingly, metals are sequestrated in various forms, defining the accumulation pattern and the magnitude of steady-state levels reached. To investigate the subcellular fractions over which Ca, Mg, Fe, Cu, Zn, Cd, Pb, Ni, and As are distributed, earthworms (Aporrectodea caliginosa) collected from the field were analyzed by isolating metal-rich granules and tissue fragments from intracellular microsomal and cytosolic fractions (i.e., heat-stable proteins and heat-denatured proteins). The fractions showed metal-specific binding capacity. Cadmium was mainly retrieved from the protein fractions. Copper was equally distributed over the protein fraction and the fraction comprising tissue fragments, cell membranes, and intact cells. Zinc, Ca, Mg, and As were mainly found in this fraction as well. Lead, Fe, and Ni were mainly isolated from the granular fraction. To study accumulation kinetics in the different fractions, three experiments were conducted in which earthworms were exposed to metal-spiked soil and a soil contaminated by anthropogenic inputs and, indigenous earthworms were exposed to field soils. Although kinetics showed variation, linear uptake and steady-state types of accumulation patterns could be understood according to subcellular compartmentalization. For risk assessment purposes, subcellular distribution of metals might allow for a more precise estimate of effects than total body burden. Identification of subcellular partitioning appears useful in determining the biological significance of steady-state levels reached in animals.

Internal metal sequestration and its ecotoxicological relevance: a review.

Organisms are able to control metal concentrations in certain tissues of their body to minimize damage of reactive forms of essential and nonessential metals and to control selective utilization of essential metals. These physiological aspects of organisms are not accounted for when assessing the risk of metals in the environment. The Critical Body Residue (CBR) approach relates toxicity to bioaccumulation and biomagnification and might at first sight provide a more accurate estimation of effects than the external concentration. When expressing CBRs on total internal concentrations, the capacity of organisms to sequester metals in forms that are not biologically reactive is neglected. The predictability of toxic effects will increase when knowledge on metal compartmentalization within the organisms' body is taken into account. Insight in metal compartmentalization sheds light on the different accumulation strategies organisms can follow upon metal exposure. Using a fractionation procedure to isolate metal-rich granules and tissue fragments from intracellular and cytosolic fractions, the internal compartmentalization of metals can be approximated. In this paper, current knowledge regarding metal compartmentalization in organisms is summarized, and metal fractions are identified that are indicators of toxicity. Guidance is provided on future improvement of models, such as the Biotic Ligand Model (BLM), for risk assessment of metal stress to biota.

Development of a terrestrial vertebrate model for assessing bioavailability of cadmium in the fence lizard (Sceloporus undulatus) and in ovo effects on hatchling size and thyroid function.

In the terrestrial environment, standardized protocols are available for measuring the exposure and effects of contaminants to invertebrates, but none currently exist for vertebrates. In an effort to address this, we proposed that developing lizard embryos may be used as a terrestrial vertebrate model. Lizard eggs may be particularly susceptible to soil contamination and in ovo exposure may affect hatchling size, mortality, as well as thyroid function. Toxicant-induced perturbations of thyroid function resulting from in ovo chemical exposure may result in toxicity during the critical perinatal period in reptiles. Fertilized Eastern fence lizard (Sceloporus undulatus) eggs were placed in cadmium (Cd)-spiked expanded perlite (0, 1.48, 14.8, 148, 1480, 14,800 microg Cd/g, nominal concentrations), artificially incubated at 28 degrees C, and examined daily for mortality. Whole lizard hatchlings as well as failed hatches were homogenized in ethanol and the homogenate was divided for Cd body residue analysis and thyroid hormone (triiodothyronine (T3) and thyroxine (T4)) analyses. Acute mortality was observed in the two highest doses (1480 and 14800 microg Cd/g). Cadmium body residues showed a higher internal concentration with increasing exposure concentration indicating uptake of Cd. There was a decrease in T3:T4 ratio at the highest surviving dose (148 microg Cd/g), however, there were no differences observed in hatchling size measured as weight and snout-vent length, or in whole body thyroid hormone levels. In summary, this study has shown Cd amended to a solid phase representing soil (perlite) can traverse the thin, parchment-like shell membrane of the fence lizard egg and bioaccumulate in lizard embryos. We believe this study is a good first step in investigating and evaluating this species for use as a model.

Method for determining toxicologically relevant cadmium residues in the earthworm Eisenia fetida.

We investigated a method to isolate toxicologically relevant Cd in earthworms (Eisenia fetida) exposed in a 14-d Cd bioaccumulation study. A procedure involving acid insoluble ash (AIA) content was combined with homogenization and centrifugation techniques to divide total earthworm Cd burdens into supernatant (metallothionein-bound), pellet (toxicologically active), and soil-associated Cd fractions. Whereas the supernatant fraction of the earthworm digests increased linearly throughout the exposure period (from approximately 0 to 3.59 mmol/kg), the pellet fraction reached a steady-state concentration (95% CI) of 1.2 (0.9-1.4) mmol/kg, suggesting the ability of the metallothionein detoxification system to sequester incoming Cd. The AIA method was useful for correcting earthworm Cd concentrations for ingested soil-associated Cd and observing soil ingestion, which was suppressed in Cd-spiked artificial soil (1.06 (0.57-1.55)%) compared to controls (17.25 (14.36-20.15)%). These methods may be useful in investigating soil ingestion and Cd uptake and detoxification in earthworms.