Lutetium speciation and toxicity in a microbial bioassay: testing the free-ion model for lanthanides

The validity of the free-ion model (FIM) for the element lutetium (Lu), a member of the lanthanides, was assessed in experiments with the bacterium Vibrio fischeri. The FIM is mainly based on divalent metals and synthetic ligands and has not yet been validated for the trivalent lanthanides. The bioluminescence response of V fischeri was studied at different Lu concentrations in the presence and absence of natural and synthetic organic ligands [citrate, malate, oxalate, acetate, ethylenediaminetetraacetate (EDTA), and nitrilotriacetate (NTA)]. All ligands were tested separately to ensure that their concentrations would not cause adverse effects themselves. Free Lu3+ concentrations were calculated with a speciation program, after extension of its database with the relevant Lu equilibria. The results confirmed the FIM for Lu: that is, in contrast to total dissolved Lu concentrations, free Lu3+ concentrations had an apparent relationship with the response of V fischeri. However, a contribution of minor inorganic Lu complexes cannot be ruled out. In the presence of malate and oxalate, the EC50 for Lu3+ decreased faster in time than for the other ligands, indicating lower elimination rates. With an EC50 Of 1.57 muM, Lu3+ is more toxic than La3+, Cd2+, or Zn2+ and approximately equally as toxic as Cu2+. Although the pH increased slightly during the experiments, it was shown that the influence of pH on Lu speciation was limited

Harnessing Modeling for Assessing the Population Relevance of Exposure to Endocrine‐Active Chemicals

Data Availability Statement: The stickleback and trout population model code and a log of changes from the original versions are available in the Supporting Information. The FOCUS output files from Toxic Substances in Surface Waters (TOXSWA) are also available, with details of how these were used in the population models.Supporting Information is available online at https://setac.onlinelibrary.wiley.com/doi/10.1002/etc.5640#support-information-section .Copyright © 2023 The Authors. The presence of endocrine-active chemicals (EACs) in the environment continues to cause concern for wildlife given their potential for adverse effects on organisms. However, there is a significant lack of understanding about the potential effects of EACs on populations. This has real-world limitations for EAC management and regulation, where the aim in environmental risk assessment is to protect populations. We propose a methodological approach for the application of modeling in addressing the population relevance of EAC exposure in fish. We provide a case study with the fungicide prochloraz to illustrate how this approach could be applied. We used two population models, one for brown trout (Salmo trutta; inSTREAM) and the other for three-spined stickleback (Gasterosteus aculeatus) that met regulatory requirements for development and validation. Effects data extracted from the literature were combined with environmentally realistic exposure profiles generated with the FOCUS SW software. Population-level effects for prochloraz were observed in some modeling scenarios (hazard-threshold [HT]) but not others (dose–response), demonstrating the repercussions of making different decisions on implementation of exposure and effects. The population responses, defined through changes in abundance and biomass, of both trout and stickleback exposed to prochloraz were similar, indicating that the use of conservative effects/exposure decisions in model parameterization may be of greater significance in determining population-level adverse effects to EAC exposure than life-history characteristics. Our study supports the use of models as an effective approach to evaluate the adverse effects of EACs on fish populations. In particular, our HT parameterization is proposed for the use of population modeling in a regulatory context in accordance with Commission Regulation (EU) 2018/605.BASF SE; UK Research and Innovation. Grant Number: MR/V025570/1

Prospective aquatic risk assessment for chemical mixtures in agricultural landscapes

Environmental risk assessment of chemical mixtures is challenging due to the multitude of possible combinations that may occur. Aquatic risk from chemical mixtures in an agricultural landscape was evaluated prospectively in two exposure scenario case studies: at field scale for a program of 13 plant protection products applied annually for 20 years, and at a watershed scale for a mixed land use scenario over 30 years with 12 plant protection products and two veterinary pharmaceuticals used for beef cattle. Risk quotients were calculated from regulatory exposure models with typical real-world use patterns and regulatory acceptable concentrations for individual chemicals. Results could differentiate situations when there was concern associated with single chemicals from those when concern was associated with a mixture (based on concentration addition) with no single chemical triggering concern. Potential mixture risk was identified on 0.02% to 7.07% of the total days modeled, depending on the scenario, the taxa and whether considering acute or chronic risk. Taxa at risk were influenced by receiving water body characteristics along with chemical use profiles and associated properties. This study demonstrates that a scenario-based approach can be used to determine whether mixtures of chemicals pose risks over and above any identified using existing approaches for single chemicals, how often and to what magnitude, and ultimately which mixtures (and dominant chemicals) cause greatest concern. This article is protected by copyright. All rights reserved

Echo of the Younger Dryas in Holocene Lake Sediments on the Tibetan Plateau

Reading the sediment record in terms of past climates is challenging since linking climate change to the associated responses of sedimentary systems is not always straightforward. Here we analyze the erosional response of landscapes on the Tibetan Plateau to interglacial climate forcing. Using the theory of dynamical systems on Holocene time series of geochemical proxies, we derive a sedimentary response model that accurately simulates observed proxy variation in three lake records. The model suggests that millennial variations in sediment composition reflect a self‐organization of landscapes in response to abrupt climate change between 11.6 and 11.9 ka BP. The self‐organization is characterized by oscillations in sediment supply emerging from a feedback between physical and chemical erosion processes, with estimated response times between 3,000 to 18,000 years depending on catchment topography. The implications of our findings emphasize the need for landscape response models to decipher the paleoclimatic code in continental sediment records

Formation and preservation of greigite (Fe₃S₄) in sediments from the Santa Barbara Basin: implications for paleoenvironmental changes during the past 35 ka

Diagenetic processes are known to modify sedimentary records, but they can also reveal important paleoenvironmental changes. Here we investigate variations in sedimentary iron diagenesis and depositional environments for the last 35 ka by analyzing the rock magnetic and geochemical properties of two sediment cores collected in the Santa Barbara Basin (California). In organic-rich sediments, early diagenesis often leads to partial dissolution of detrital iron oxides and stepwise formation of authigenic pyrite (FeS2). The pyritization process takes place following several geochemical pathways, sometimes involving intermediate iron sulfide species such as greigite (Fe3S4). Sedimentary conditions in the basin appear to have recurrently favored preservation of greigite (identified by its magnetic properties) and inhibited its complete transformation into pyrite. The Holocene interval contains a series of centimeter-thick greigite-bearing layers that are associated with large flood deposits, which are known in the basin as ‘‘gray layers.’’ We propose that greigite preservation was enabled in these sediments by their relative enrichment in reactive iron over organic matter and/or hydrogen sulfide (because of their high ratio of terrigenous over organic material), which limited pyritization reactions. Within the glacial deposits, formation and preservation of meter-thick greigite layers occurred in terrigenous-rich and organic-poor sedimentary layers and is proposed to result from a similar diagenetic process to that in the Holocene greigite-bearing layers (dominance of reactive iron over organic matter and/or HS�). The terrigenous enrichments in the glacial greigite-bearing layers are probably related to climatic or sea level changes because they occur at times of massive iceberg releases in the North Atlantic, the so-called Heinrich events

Eliciting Dirichlet and Gaussian copula prior distributions for multinomial models

In this paper, we propose novel methods of quantifying expert opinion about prior distributions for multinomial models. Two different multivariate priors are elicited using median and quartile assessments of the multinomial probabilities. First, we start by eliciting a univariate beta distribution for the probability of each category. Then we elicit the hyperparameters of the Dirichlet distribution, as a tractable conjugate prior, from those of the univariate betas through various forms of reconciliation using least-squares techniques. However, a multivariate copula function will give a more flexible correlation structure between multinomial parameters if it is used as their multivariate prior distribution. So, second, we use beta marginal distributions to construct a Gaussian copula as a multivariate normal distribution function that binds these marginals and expresses the dependence structure between them. The proposed method elicits a positive-definite correlation matrix of this Gaussian copula. The two proposed methods are designed to be used through interactive graphical software written in Java

Combinations of physiologic estrogens with xenoestrogens alter calcium and kinase responses, prolactin release, and membrane estrogen receptor trafficking in rat pituitary cells

<p>Abstract</p> <p>Background</p> <p>Xenoestrogens such as alkylphenols and the structurally related plastic byproduct bisphenol A have recently been shown to act potently via nongenomic signaling pathways and the membrane version of estrogen receptor-α. Though the responses to these compounds are typically measured individually, they usually contaminate organisms that already have endogenous estrogens present. Therefore, we used quantitative medium-throughput screening assays to measure the effects of physiologic estrogens in combination with these xenoestrogens.</p> <p>Methods</p> <p>We studied the effects of low concentrations of endogenous estrogens (estradiol, estriol, and estrone) at 10 pM (representing pre-development levels), and 1 nM (representing higher cycle-dependent and pregnancy levels) in combinations with the same levels of xenoestrogens in GH₃/B6/F10 pituitary cells. These levels of xenoestrogens represent extremely low contamination levels. We monitored calcium entry into cells using Fura-2 fluorescence imaging of single cells. Prolactin release was measured by radio-immunoassay. Extracellular-regulated kinase (1 and 2) phospho-activations and the levels of three estrogen receptors in the cell membrane (ERα, ERβ, and GPER) were measured using a quantitative plate immunoassay of fixed cells either permeabilized or nonpermeabilized (respectively).</p> <p>Results</p> <p>All xenoestrogens caused responses at these concentrations, and had disruptive effects on the actions of physiologic estrogens. Xenoestrogens reduced the % of cells that responded to estradiol via calcium channel opening. They also inhibited the activation (phosphorylation) of extracellular-regulated kinases at some concentrations. They either inhibited or enhanced rapid prolactin release, depending upon concentration. These latter two dose-responses were nonmonotonic, a characteristic of nongenomic estrogenic responses.</p> <p>Conclusions</p> <p>Responses mediated by endogenous estrogens representing different life stages are vulnerable to very low concentrations of these structurally related xenoestrogens. Because of their non-classical dose-responses, they must be studied in detail to pinpoint effective concentrations and the directions of response changes.</p