Recent efforts have been directed towards better understanding the persistency and toxicity of ionic liquids (ILs) in the context of the “benign-by-design” approach, but the assessment of their bioaccumulation potential remains neglected. This paper reports the experimental membrane partitioning of IL cations (imidazolium, pyridinium, pyrrolidinium, phosphonium), anions ([C(CN)3]-, [B(CN)4]-, [FSO2)2N]-, [(C2F5)3PF3]-, [(CF3SO2)2N]-) and their combinations as a measure for estimating the bioconcentration factor (BCF). Both cations and anions can have a strong affinity for phosphatidylcholine bilayers, which is mainly driven by the hydrophobicity of the ions. This affinity is often reflected in the ecotoxicological impact. Our data revealed that the bioconcentration potential of IL cations and anions is much higher than expected from octanol-water-partitioning based estimations that have recently been presented. For some ILs, the membrane-water partition coefficient reached levels corresponding to BCFs that might become relevant in terms of the “B” (bioaccumulation potential) classification under REACH. However, this preliminary estimation need to be confirmed by in vivo bioconcentration studies.

The Catskill Mountains have been adversely impacted by decades of acid deposition, however, since the early 1990s, levels have decreased sharply as a result of decreases in emissions of sulfur dioxide and nitrogen oxides. This study examines trends in acid deposition, stream-water chemistry, and soil chemistry in the southeastern Catskill Mountains. We measured significant reductions in acid deposition and improvement in stream-water quality in 5 streams included in this study from 1992 to 2014. The largest, most significant trends were for sulfate (SO42−) concentrations (mean trend of −2.5 μeq L−1 yr−1); hydrogen ion (H+) and inorganic monomeric aluminum (Alim) also decreased significantly (mean trends of −0.3 μeq L−1 yr−1 for H+ and −0.1 μeq L−1 yr−1 for Alim for the 3 most acidic sites). Acid neutralizing capacity (ANC) increased by a mean of 0.65 μeq L−1 yr−1 for all 5 sites, which was 4 fold less than the decrease in SO42− concentrations. These upward trends in ANC were limited by coincident decreases in base cations (−1.3 μeq L−1 yr−1 for calcium + magnesium). No significant trends were detected in stream-water nitrate (NO3−) concentrations despite significant decreasing trends in NO3− wet deposition. We measured no recovery in soil chemistry which we attributed to an initially low soil buffering capacity that has been further depleted by decades of acid deposition. Tightly coupled decreasing trends in stream-water silicon (Si) (−0.2 μeq L−1 yr−1) and base cations suggest a decrease in the soil mineral weathering rate. We hypothesize that a decrease in the ionic strength of soil water and shallow groundwater may be the principal driver of this apparent decrease in the weathering rate. A decreasing weathering rate would help to explain the slow recovery of stream pH and ANC as well as that of soil base cations.

Laccase is a widely present extracellular phenoloxidase excreted by fungi, bacteria, and high plants. It is able to catalyze one-electron oxidation of phenolic compounds into radical intermediates that can subsequently couple to each other via covalent bonds. These reactions are believed to play an important role in humification process and the transformation of contaminants containing phenolic functionalities in the environment. In this study, we investigated the kinetics of triclosan transformation catalyzed by laccase. It was found that the rate of triclosan oxidation was first order to the concentrations of both substrate and enzyme. Humic acid (HA) could inhibit the reaction by quenching the radical intermediate of triclosan generated by laccase oxidation. Such inhibition was more significant in the presence of divalent metal cations. This is because that binding to metal ions neutralized the negative charge of HA molecules, thus making them more accessible to laccase molecule that is also negatively charged. Therefore, it has greater chance to quench the radical intermediate that is very unstable and can only diffuse a limited distance after being released from the enzyme catalytic center. Based on these understandings, a reaction model was developed by integration of metal-HA binding equilibriums and kinetic equations. This model precisely predicted the transformation rate of triclosan in the presence of HA and divalent metal ions including Ca2+, Mg2+, Cd2+, Co2+, Mn2+, Ba2+, and Zn2+. Overall, this work reveals important insights into laccase catalyzed oxidative coupling process.

Lead (Pb) contaminated soils are a potential exposure hazard to the public. Amending soils with phosphorus (P) may reduce Pb soil hazards. Soil from Cleveland, OH containing 726 ± 14 mg Pb kg⁻¹ was amended in a laboratory study with bone meal and triple super phosphate (TSP) at 5:1 P:Pb molar ratios. Soil was acidified, neturalized and re-acidified to encourage Pb phosphate formation. PRSTM-probes were used to evaluate changes in soil solution chemistry. Soil acidification did not decrease in vitro bioaccessible (IVBA) Pb using either a pH 1.5, 0.4 M glycine solution or a pH 2.5 solution with organic acids. PRSTM-probe data found soluble Pb increased 10-fold in acidic conditions compared to circumnetural pH conditions. In acidic conditions (p = 3-4), TSP treated soils increased detected P 10-fold over untreated soils. Bone meal application did not increase PRSTM-probe detected P, indicating there may have been insufficient P to react with Pb. X-ray absorption spectroscopy suggested a 10% increase in pyromorphite formation for the TSP treated soil only. Treatments increased soil electrical conductivity above 16 mS cm⁻¹, potentially causing a new salinity hazard. This study used a novel approach by combining the human ingestion endpoint, PRSTM-probes, and X-ray absorption spectroscopy to evaluate treatment efficacy. PRSTM-probe data indicated potentially excess Ca relative to P across incubation steps that could have competed with Pb for soluble P. More research is needed to characterize soil solutions in Pb contaminated urban soils to identify where P treatments might be effective and when competing cations, such as Ca, Fe, and Zn may limit low rate P applications for treating Pb soils.

With the extensive application of graphene oxide (GO), it is noticeable that part of GO is directly/indirectly released into the environment and widespread research indicated that it had adverse influences on human health and ecological balance. In this work, a novel nanobelt-like Ca/Al layered double hydroxides (CA-LDH) was synthesized and applied as efficient coagulant for the removal of GO from aqueous solutions. The results indicated that neutral pH, co-existing cations and higher temperature were beneficial to the coagulation of GO. The sequence of cation effect for promoting of GO coagulation was Ca2+ > Mg2+ > K+ > Na+, whereas the effect of anions on GO coagulation was PO43− > CO32− > SO42− > Cl−. Comparing with anions, the cations showed more dominate effect for GO coagulation than anions. Hydrogen bonds and electrostatic interaction were the main coagulation mechanisms for GO coagulation, which were evidenced by FT-IR and XPS analysis. Specifically, for the first time, the reclaimed product of CA-LDH after GO coagulation (CA-LDH + GO) was applied as adsorbents for the secondary application in the removal of heavy metal ions from aqueous solutions. Interestingly, the CA-LDH + GO still had high adsorption capacities, i.e., the maximum adsorption capacities (qmax) for Cu(II), Pb(II), and Cr(VI) were 122.7 mg/g, 221.2 mg/g and 64.4 mg/g, respectively, higher than other similar materials. This paper highlighted the LDH-based nanomaterials are promising materials for the elimination of environmental pollutants and the migration and transformation of carbon nanomaterials in the natural environment.

This study aimed to investigate the difference of osmoregulation between two edible amaranth cultivars, Liuye (high Cd accumulator) and Quanhong (low Cd accumulator), under salinity stress and determine the effects of such difference on Cd accumulation. A pot experiment was conducted to expose the plants to sewage-irrigated garden soil (mean 2.28 mg kg⁻¹ Cd) pretreated at three salinity levels. Under salinity stress, the concentrations of Cd in the two cultivars were significantly elevated compared with those in the controls, and the Cd concentration in Liuye was statistically higher than that in Quanhong (p < 0.05). Salinity-induced osmoregulation triggered different biogeochemical processes involved in Cd mobilization in the rhizosphere soil, Cd absorption, and translocation by the two cultivars. Rhizosphere acidification induced by an imbalance of cation over anion uptake was more serious in Liuye than in Quanhong, which obviously increased soil Cd bioavailability. Salinity-induced injuries in the cell wall pectin and membrane structure were worse in Liuye than in Quanhong, increasing the risk of Cd entering the protoplasts. The chelation of more cytoplasmic Cd²⁺ with Cl⁻ ions in the roots of Liuye promoted Cd translocation into the shoots. Furthermore, the less organic solutes in the root sap of Liuye than in that of Quanhong also favored Cd translocation into the shoots. Hence, osmoregulation processes can be regarded as important factors in reducing Cd accumulation in crop cultivars grown on saline soils.

Precipitation samples have been collected by the National Atmospheric Deposition Program's (NADP) National Trends Network (NTN) using the Aerochem Metrics Model 301 (ACM) collector since 1978. Approximately one-third of the NTN ACM collectors have been replaced with N-CON Systems, Inc. Model ADS 00-120 (NCON) collectors. Concurrent data were collected over 6 years at 12 NTN sites using colocated ACM and NCON collectors in various precipitation regimes. Linear regression models of the colocated data were used to adjust for relative bias between the collectors. Replacement of ACM collectors with NCON collectors resulted in shifts in 10-year seasonal precipitation-weighted mean concentration (PWMC) trend slopes for: cations (−0.001 to −0.007 mgL−1yr−1), anions (−0.009 to −0.028 mgL−1yr−1), and hydrogen ion (+0.689 meqL-1yr−1). Larger shifts in NO3− and SO4−2 seasonal PWMC trend slopes were observed in the Midwest and Northeast US, where concentrations are generally higher than in other regions. Geospatial analysis of interpolated concentration rasters indicated regions of accentuated variability introduced by incorporation of NCON collectors into the NTN.

The use of road deicing salts in regions that experience cold winters is increasing the salinity of freshwater ecosystems, which threatens freshwater resources. Yet, the impacts of environmentally relevant road salt concentrations on freshwater organisms are not well understood, particularly in stream ecosystems where salinization is most severe. We tested the impacts of deicing salts—sodium chloride (NaCl), magnesium chloride (MgCl2), and calcium chloride (CaCl2)—on the growth and development of newly hatched rainbow trout (Oncorhynchus mykiss). We exposed rainbow trout to a wide range of environmentally relevant chloride concentrations (25, 230, 860, 1500, and 3000 mg Cl− L−1) over an ecologically relevant time period (25 d). We found that the deicing salts studied had distinct effects. MgCl2 did not affect rainbow trout growth at any concentration. NaCl had no effects at the lowest three concentrations, but rainbow trout length was reduced by 9% and mass by 27% at 3000 mg Cl− L−1. CaCl2 affected rainbow trout growth at 860 mg Cl− L−1 (5% reduced length; 16% reduced mass) and these effects became larger at higher concentrations (11% reduced length; 31% reduced mass). None of the deicing salts affected rainbow trout development. At sub-lethal and environmentally relevant concentrations, our results do not support the paradigm that MgCl2 is the most toxic deicing salt to fish, perhaps due to hydration effects on the Mg2+ cation. Our results do suggest different pathways for lethal and sub-lethal effects of road salts. Scaled to the population level, the reduced growth caused by NaCl and CaCl2 at critical early-life stages has the potential to negatively affect salmonid recruitment and population dynamics. Our findings have implications for environmental policy and management strategies that aim to reduce the impacts of salinization on freshwater organisms.

Current risk assessment models for metals such as the biotic ligand model (BLM) are usually applied to individual metals, yet toxic metals are rarely found singly in the environment. In the present research, the toxicity of Cu and Zn alone and together were studied in wheat (Triticum aestivum L.) using different Ca2+ and Mg2+ concentrations, pH levels and Zn:Cu concentration ratios. The aim of the study was to better understand the toxicity effects of these two metals using BLMs and toxic units (TUs) from single and combined metal toxicity data. The results of single-metal toxicity tests showed that toxicity of Cu and Zn tended to decrease with increasing Ca2+ or Mg2+ concentrations, and that the effects of pH on Cu and Zn toxicity were related not only to free Cu2+ and Zn2+ activity, respectively, but also to other inorganic metal complex species. For the metal mixture, Cu–Zn interactions based on free ion activities were primarily additive for the different Ca2+ and Mg2+ concentrations and levels of pH. The toxicity data of individual metals derived by the BLM, which incorporated Ca2+ and Mg2+ competition and toxicity of inorganic metal complexes in a single-metal toxicity assessment, could predict the combined toxicity as a function of TU. There was good performance between the predicted and observed effects (root mean square error [RMSE] = 7.15, R2 = 0.97) compared to that using a TU method with a model based on free ion activity (RMSE = 14.29, R2 = 0.86). The overall findings indicated that bioavailability models that include those biochemistry processes may accurately predict the toxicity of metal mixtures.

Here we characterized wet deposition National Atmospheric Deposition Program (NADP) species and Clean Air Status and Trends Network (CASTNET) dry deposited particle and gas species across New York over the last 2-3 decades. In addition measurements of NH3 from the Ammonia Monitoring Network (AMoN) were analyzed. In general decreasing annual trends are observed for wet deposition SO42− and NO3− species and dry deposited particle SO42−, NO3− and NH4+ as well as gas phase SO2 and HNO3 consistent with reductions in SO2 and NOx emissions. Wet deposited NH4+ however does not show consistent trends with most sites showing little trend across the region and an indication that levels at some sites maybe increasing. NH3 concentrations also appear to be increasing although the data record is only 8 years. Base cations, Ca2+ and Mg2+ show some decreases in the 1980s but concentrations are relatively uniform since the mid-1990s. Na+ and K+ show large year to year variations, by more than an order of magnitude for Na+ due to influence of marine air at a near coastal site. In general there was a balance between the sum of cations and the sum of anions earlier in the record but the tendency has been for a cation excess in the more recent 5–10 years. Understanding the deposition of reduced nitrogen species is likely to be of concern for the foreseeable future. Such data are important in understanding acidification recovery in response to emission controls.