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Novel flame retardants (FRs) are of increasing concern, given growing evidence of health effects and use to replace polybrominated diphenyl ethers (PBDEs). This study modeled combined effects of use policies and decoration on indoor FRs and human exposure for 18 widely used PBDEs, organophosphate esters (OPEs), and novel brominated flame retardants in typical urban indoor environments in China. The current estimated indoor emission rates and average concentrations in air and dust of the 18 FRs were 102-103 ng/h, 561 ng/m3, and 1.5 × 104 ng/g, respectively, with seven OPEs dominant (>69%). Different use patterns exist between China and the US and Europe. Scenarios modeled over 2010-2030 suggested that decoration would affect indoor concentrations of FRs more than use policies, and use policies were mainly responsible for shifts of FR composition. Additional use of hexabromobenzene and 2,3,4,5,6-pentabromotoluene and removal of BDE-209 would make the total human exposure to the modeled FR mixture increase after the restriction of penta- and octa-BDE but decrease after deca-BDE was banned. Better knowledge of the toxicity of substitutes is needed for a complete understanding of the health implications of such changes. Toddlers may be more affected by use changes than adults. Such studies are supportive to the management of FR use.

Land application of wastes from concentrated animal feeding operations results in accumulation of copper (Cu) and antimicrobials in terrestrial systems. Interaction between Cu and antimicrobials may change Cu speciation in soil solution, and affect Cu bioavailability and toxicity. In this study, earthworms were exposed to quartz sand percolated with different concentrations of Cu and ciprofloxacin (CIP). Copper uptake by earthworms, its subcellular partition, and toxicity were studied. An increase in the applied CIP decreased the free Cu ion concentration in external solution and mortalities of earthworm, while Cu contents in earthworms increased. Copper and CIP in earthworms were fractionated into five fractions: a granular fraction (D), a fraction consisting of tissue fragments, cell membranes, and intact cells (E), a microsomal fraction (F), a denatured proteins fraction (G), and a heat-stable proteins fraction (H). Most of the CIP in earthworms was in fraction H. Copper was redistributed from the metal-sensitive fraction E to fractions D, F, G, and H with increasing CIP concentration. These results challenge the free ion activity model and suggested that Cu may be partly taken up as Cu-CIP complexes in earthworms, changing the bioavailability, subcellular distribution, and toxicity of Cu to earthworms.

There are currently few studies on the dual effects of metal ions on the sorption of atrazine and conversely of atrazine on metal adsorption on multiwalled carbon nanotubes (MWCNTs). While a number of sorption models were considered to describe the sorption of atrazine on MWCNTs, the Polanyi-Manes model (PMM) fit the sorption isotherms well with the lowest mean weighted square errors. Atrazine was mainly adsorbed onto the surface and micropores of MWCNTs bundles or aggregates. Hydrogen bonding between azo and amino nitrogen of atrazine and functional groups on MWCNTs also occurred. Oxygenated functionalities, mainly carboxylic groups on MWCNTs surface, decreased the sorption of atrazine. Metal cations Cu2+, Pb2+, and Cd2+ diminished the sorption of atrazine depending on the oxygenated functionalities densities. The mechanisms ascribed were due to the formation of surface or inner-sphere complexes of Cu2+, Pb2+, and Cd2+ through carboxylic groups and hydration, which may occupy part of the surface of MWCNTs-O. The large hydration shell of metal cations may intrude or shield the hydrophobic and hydrophilic sites and indirectly compete with atrazine for surface sites, leading to the inhibition of atrazine adsorption around the metal-complexed moieties.