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Bioconcentration of Organotin Cations during Molting Inhibits Heterocypris incongruens Growth.

ABSTRACT: The densely populated North Sea region encompasses catchments of rivers such as Scheldt and Meuse. Herein, agricultural, industrial, and household chemicals are emitted, transported by water, and deposited in sediments, posing ecological risks. Though sediment monitoring is often costly and time-intensive, modeling its toxicity to biota has received little attention. Due to high complexity of interacting variables that induce overall toxicity, monitoring data only sporadically validates current models. Via a range of concepts, we related bio-physicochemical constituents of sediment in Flanders to results from toxicity bioassays performed on the ostracod Heterocypris incongruens. Depending on the water body, we explain up to 90% of the variance in H. incongruens growth. Though variable across Flanders' main water bodies, organotin cations and ammonia dominate the observed toxicity according to toxic unit (TU) assessments. Approximately 10% relates to testing conditions/setups, species variabilities, incoherently documented pollutant concentrations, and/or bio-physicochemical sediment properties. We elucidated the influence of organotin cations and ammonia relative to other metal(oxides) and biocides. Surprisingly, the tributylin cation appeared ?1000 times more toxic to H. incongruens as compared to "single-substance" bioassays for similar species. We inferred indirect mixture effects between organotin, ammonia, and phosphate. Via chemical speciation calculations, we observed strong physicochemical and biological interactions between phosphate and organotin cations. These interactions enhance bioconcentration and explain the elevated toxicity of organotin cations. Our study aids water managers and policy makers to interpret monitoring data on a mechanistic basis. As sampled sediments differ, future modeling requires more emphasis on characterizing and parametrizing the interactions between bioassay constituents. We envision that this will aid in bridging the gap between testing in the laboratory and field observations.

SUBMITTER: Nolte TM

PROVIDER: S-EPMC7685533 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Bioconcentration of Organotin Cations during Molting Inhibits <i>Heterocypris incongruens</i> Growth.

Nolte Tom M TM De Cooman Ward W Vink Jos P M JPM Elst Raf R Ryken Els E Ragas Ad M J AMJ Hendriks A Jan AJ

Environmental science & technology 20201102 22

The densely populated North Sea region encompasses catchments of rivers such as Scheldt and Meuse. Herein, agricultural, industrial, and household chemicals are emitted, transported by water, and deposited in sediments, posing ecological risks. Though sediment monitoring is often costly and time-intensive, modeling its toxicity to biota has received little attention. Due to high complexity of interacting variables that induce overall toxicity, monitoring data only sporadically validates current ...[more]

PMID: 33135409

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Project description:Since their first description over a decade ago, organotin(ii) hydrides have been an iconic class of compounds in molecular main group chemistry. Among other approaches they have been accessed from the hydrogenation of distannynes. We herein report their accessibility from the other direction by dehydrogenation of organotin trihydride. On reacting pyridine and amine bases with the bulky substituted organotin trihydride Ar*SnH3 (Ar* = 2,6-trip2(C6H3)-, trip = 2,4,6-triisopropylphenyl) hydrogen evolution was observed. In case of catalytic amounts of base the dehydro-coupling product diorganodistannane Ar*H2SnSnH2Ar* was obtained quantitatively whilst for excessive amounts (>4 eq.) the monomeric base adduct to known Ar*SnH was obtained almost exclusively. The base adducts were found to be remarkably thermally robust. They readily react with polar fulvenic C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C-bonds in hydro-stannylenylation reactions. The resulting half-sandwich complex Ar*SnCp* was structurally characterized. Moreover, on application of less nucleophilic amine bases, the uncoordinated, in solution dimeric [Ar*SnH]2 is formed. NMR spectroscopic studies on the kinetics of the DMAP-catalysed reductive elimination of dihydrogen were performed. The activation energy was approximated to be 13.7 kcal mol-1. Solvent dependencies and a kinetic isotope effect KIE of kH/kD = 1.65 in benzene and 2.04 in THF were found and along with DFT calculations support a polar mechanism for this dehydrogenation.

Dataset Information

Bioconcentration of Organotin Cations during Molting Inhibits Heterocypris incongruens Growth.

Publications

Bioconcentration of Organotin Cations during Molting Inhibits <i>Heterocypris incongruens</i> Growth.

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