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Fluctuation exposure of trace metal copper (Cu) is ubiquitous in aquatic environments. The purpose of this study was to investigate the impacts of chronically pulsed exposure on biodynamics and subcellular partitioning of Cu in freshwater tilapia (Oreochromis mossambicus). Long-term 28-day pulsed Cu exposure experiments were performed to explore subcellular partitioning and toxicokinetics/toxicodynamics of Cu in tilapia. Subcellular partitioning linking with a metal influx scheme was used to estimate detoxification and elimination rates. A biotic ligand model-based damage assessment model was used to take into account environmental effects and biological mechanisms of Cu toxicity. We demonstrated that the probability causing 50% of susceptibility risk in response to pulse Cu exposure in generic Taiwan aquaculture ponds was ~33% of Cu in adverse physiologically associated, metabolically active pool, implicating no significant susceptibility risk for tilapia. We suggest that our integrated ecotoxicological models linking chronic exposure measurements with subcellular partitioning can facilitate a risk assessment framework that provides a predictive tool for preventive susceptibility reduction strategies for freshwater fish exposed to pulse metal stressors.

This study successfully applied an improved valvometry technique to measure waterborne copper (Cu), based on valve activity dynamics of the freshwater clam Corbicula fluminea. The improved valvometry technique allows the use of free-range bivalves and avoids causing stresses from experimental artifacts. The proposed daily valve rhythm models and a toxicodynamics-based Hill model were linked to predict valve dynamic responses under different Cu exposures with a circadian valve rhythm endpoint. Cu-specific detection threshold was 5.6 (95 % CI 2.1-9.3) and 19.5 (14.6-24.3) μg L(-1) for C. fluminea, based on response times of 300 and 30 min, respectively. Upon exposure to Cu concentrations in excess of 50 μg L(-1), the alteration of valve rhythm behavior was correlated with Cu concentration within 30 min, indicating notable sensing ability. This study outlines the feasibility of an in situ early warning dynamic biomonitoring system for detection of waterborne Cu based on circadian valve activities of C. fluminea.

Branchial Na(＋)-K(＋)-ATPase (NKA) activity has been suggested as a promising biomarker for assessing metal stress in aquatic organisms. However, studies that systematically show the effectiveness of using NKA activity to detect metal exposure and toxicity at the individual level are limited. In this study, we aimed to determine whether branchial NKA activity mechanistically responds to the accumulation of waterborne copper (Cu) and accounts for observed toxicity over time under environmentally-relevant and aquafarming Cu exposure levels (0.2, 1 and 2 mg L(-1)). Temporal trends in Cu accumulation and the corresponding responses of branchial NKA activity resulting from Cu exposure were investigated in laboratory experiments conducted on juvenile tilapia (Oreochromis mossambicus), a freshwater teleost that shows potential as a bioindicator of real-time and historical metal pollution. We used the process-based damage assessment model (DAM) to inspect the time course of Cu toxicity by integrating the compensation process between Cu-induced inhibition and repair of branchial NKA activity. NKA activity acted as a sensitive biomarker for Cu exposure and accumulation in tilapia, which showed induced impairment of osmoregulation and lethality when they were exposed to environmentally relevant levels (0.2 mg L(-1)), but not to higher exposure levels (1 and 2 mg L(-1)) in aquaculture farms or contaminated aquatic ecosystems. This study highlights the benefits and limitations of using branchial NKA activity as a sensitive biomarker to assess the health status of a fish population and its ecosystem., (Copyright © 2015 Elsevier B.V. All rights reserved.)

To understand how environmental variability could impose aquatic organisms in response to altered disturbance regimes and temporal patterns of waterborne toxicants is challenging. Few studies have reported in an organ/tissue specific basis, and most studies have been restricted to steady-state conditions. For interpreting systematically copper (Cu) bioaccumulation in tilapia (Oreochromis mossambicus) in a pulse scheme, we combined mechanistic and statistical as well as model-based data analyses of exposure data that cover short-term mortality to long-term organ/tissue growth bioassay. Our present pulsed Cu-tilapia physiologically-based pharmacokinetic model was capable of elucidating the Cu accumulation dynamics in tissues of tilapia under different pulsed exposure scenarios. Under acute and chronic pulsed exposures, our study found that (i) stomach and kidney had the highest uptake and elimination capacities, (ii) liver was prone to a highest BCF and was more sensitive than the other tissues, and (iii) Cu accumulations in most of organs and other tissues were strongly dependent on the exposure pulse characteristics such as frequency and duration and not on concentration (i.e., amplitude). We showed that interactions across multiple pulsed or fluctuating Cu exposures were involved in accumulation changes that could also be achieved by controlling pulse timing and duration. The analytical approach we described provides an opportunity to examine and quantify metal accumulation dynamics for fish in response to environmental variability-induced non-uniform metal exposures on an organ/tissue-dependent scale and to integrate qualitative information with toxicokinetic and physiological data. We hope that our systems-level tools for mathematical analyses and modeling will facilitate future large-scale and dynamic systems biology studies in other model fish.

One of the major challenges in assessing the potential metal stress to aquatic organisms is explicitly predicting the internal dose in target organs. We aimed to understand the main sources of copper (Cu) accumulation in target organs of tilapia (Oreochromis mossambicus) and to investigate how the fish alter the process of Cu uptake, depuration, and accumulation (toxicokinetics (TK)) under prolonged conditions. We measured the temporal Cu profiles in selected organs after single and combined exposure to waterborne and dietary Cu for 14 days. Quantitative relations between different sources and levels of Cu, duration of treatment, and organ-specific Cu concentrations were established using TK modeling approaches. We show that water was the main source of Cu in the gills (>94 %), liver (>89 %), and alimentary canal (>86 %); the major source of Cu in the muscle (>51 %) was food. Cu uptake and depuration in tilapia organs were mediated under prolonged exposure conditions. In general, the uptake rate, depuration rate, and net bioaccumulation ability in all selected organs decreased with increasing waterborne Cu levels and duration of exposure. Muscle played a key role in accounting for the rapid Cu accumulation in the first period after exposure. Conversely, the liver acted as a terminal Cu storage site when exposure was extended. The TK processes of Cu in tilapia were highly changed under higher exposure conditions. The commonly used bioaccumulation model might lead to overestimations of the internal metal concentration with the basic assumption of constant TK processes.

The impact of environmentally pulsed metal exposure on population dynamics of aquatic organisms remains poorly understood and highly unpredictable. The purpose of our study was to link a dynamic energy budget model to a toxicokinetic/toxicodynamic (TK/TD). We used the model to investigate tilapia population dynamics in response to pulsed waterborne copper (Cu) assessed with available empirical data. We mechanistically linked the acute and chronic bioassays of pulsed waterborne Cu at the scale of individuals to tilapia populations to capture the interaction between environment and population growth and reproduction. A three-stage matrix population model of larva-juvenile-adult was used to project offspring production through two generations. The estimated median population growth rate (λ) decreased from 1.0419 to 0.9991 under pulsed Cu activities ranging from 1.6 to 2.0 μg L(-1). Our results revealed that the influence on λ was predominately due to changes in the adult survival and larval survival and growth functions. We found that pulsed timing has potential impacts on physiological responses and population abundance. Our study indicated that increasing time intervals between first and second pulses decreased mortality and growth inhibition of tilapia populations, indicating that during long pulsed intervals tilapia may have enough time to recover. Our study concluded that the bioenergetics-based matrix population methodology could be employed in a life-cycle toxicity assessment framework to explore the effect of stage-specific mode-of-actions in population response to pulsed contaminants.

The manufacture of large quantities of engineered nanomaterials (NMs) may lead to unintended contamination of aquatic ecosystems. Biologically based monitoring techniques need to be developed to detect these emerging NMs. The purpose of this study was to develop a risk-based probability model to predict the potential hazards of nanoecotoxicity toward aquatic organisms posed by waterborne copper and silver nanoparticles (Cu/Ag NPs). Published experimental evidence based on Cu/Ag NP-zebrafish (Danio rerio) systems was adopted as the study data. A Hill model was used to reconstruct a concentration-mortality response profile. A cumulative Weibull predictive model was employed to estimate exposure thresholds. The derived probabilistic model can predict the potential risk of environmentally relevant Cu/Ag NPs for major Taiwanese rivers with predicted environmental concentrations of 0.06 (95% confidence interval (CI): 0.01-0.92) mgL(-1) for Cu NPs and 0.04 (0.01-0.11) mgL(-1) for Ag NPs. The results indicated that estimated thresholds were 0.10-0.48mgL(-1) (95% CI) for Cu NPs and 2.69-2.73mgL(-1) for Ag NPs. The probabilities of a risk quotient (RQ) of >1 ranged 17%-81% for zebrafish exposed to Cu NPs. This study found that Ag NP exposure scenarios posed no significant risks to zebrafish (RQ≪0.1)., (Copyright © 2012 Elsevier B.V. All rights reserved.)

The impact of environmentally pulsed metal exposure on aquatic organisms is poorly understood experimentally. The purpose of this study was to provide an analysis methodology for assessing the effects of pulsed waterborne copper (Cu) on life-stage tilapia populations. We conducted 10-day exposure experiments to obtain toxicokinetic parameters for larva, juvenile, and adult tilapia exposed to pulsed Cu. We linked threshold damage model and biotic ligand model to assess the survival probability for tilapia populations to pulsed Cu exposure. Here we showed that the change in exposure patterns did change substantially survival rates for each life stage of tilapia. We indicated that an apparent difference in time course of survival probability between pulsed and constant Cu exposures was found in each life stage. We concluded that the life-stage factor needs to be incorporated into studies of species interactions under different disturbance regimes. This study suggested that life-stage-specific toxicokinetic parameters and adequate water chemistry might be important to consider in risk assessment of population survivorship for aquatic species under pulsed exposure scenarios., (Copyright © 2011 Elsevier B.V. All rights reserved.)

A simple strategy for the preparation of strongly fluorescent and stable DNA-Cu/Ag NCs from reduction of AgNO(3) and Cu(NO(3))(2) by NaBH(4) in the presence of DNA having a sequence 5'-CCCTTAATCCCC-3' has been demonstrated. Fluorescence, absorption, X-ray photoelectron spectroscopy (XPS), and electrospray ionization-mass spectrometry (ESI-MS) measurements have been applied to the characterization of the DNA-Cu/Ag NCs. The ESI-MS data reveal that each DNA-Cu/Ag NC contained 2 Ag and 1 Cu atoms. The interactions among DNA with the Ag and Cu atoms are further supported by the data of low-temperature fluorescence. In the presence of Cu(2+) ions, the reaction time is 1.5 h, which is much shorter than that (120 h) for the preparation of Ag-DNA NCs that are prepared in a mixture of AgNO(3), NaBH(4) and DNA without containing Cu(2+) ions. Relative to the DNA-Ag NCs, the DNA-Cu/Ag NCs have greater fluorescence (quantum yield 51.2% vs. 11.5%). The DNA-Cu/Ag NCs are highly sensitive and selective for the detection of single-stranded DNA binding protein (SSB), with a linear range 1-50 nM and a limit of detection 0.2 nM at a signal-to-ratio of 3.

We have developed a simple and homogeneous fluorescence assay, comprised of 3-mercaptopropionic acid (MPA) and DNA-Cu/Ag nanoclusters (NCs) in aqueous solution, for the detection of Cu(2+) ions. The fluorescence of the DNA-Cu/Ag NCs was quenched by MPA, which was recovered in the presence of Cu(2+) ions. This MPA-induced fluorescence quenching arises through changes in the DNA conformation that occur after interactions between MPA and the Cu/Ag clusters. The MPA-induced fluorescence quenching displayed typical characteristics in Stern-Volmer plots; it followed a static quenching mechanism. The presence of Cu(2+) ions resulted in the oxidation of MPA to form a disulfide compound, leading to recovery of the fluorescence of the DNA-Cu/Ag NCs. The fluorescence of the DNA-Cu/Ag NCs in the presence of MPA increased upon increasing the concentration of Cu(2+) ions over the range from 5 to 200 nM. The DNA-Cu/Ag NC probe provided the limit of detection (at a signal-to-noise ratio of 3) for Cu(2+) ions of 2.7 nM, with high selectivity (by at least 2300-fold over other tested metal ions). We validated the practicality of using this probe for the detection of Cu(2+) ions in environmental samples through analyses of Montana soil and pond water samples.

This study investigated the microstructure and grain orientation of Ni(V)/SAC396/OSP Cu and Ni(V)/SAC105/OSP Cu solder joints during thermal cycling test (TCT). In general, adjusting Ag content in solders influenced the performance of thermal cycling (TC). Nevertheless, it is still crucial to find the optimal condition of Ag and related mechanisms of crack formation during TCT. This study applied FE-SEM to observe the crack propagation and the precipitation of Sn-Ag IMCs in the solders. Moreover, FE-EPMA and EBSD were used to detect the elemental distribution and grain orientation near the cracks, respectively. The locations of crack initiation are strongly related to the CTE mismatch between Si chip and solder alloy. Besides, the large number of AgSn precipitations in the joint with high Ag content efficiently hinder the crack propagation due to the effects of precipitation hardening. It is revealed that the Ni(V)/SAC396/OSP Cu exhibits good thermal stability during thermal cycle test. [ABSTRACT FROM AUTHOR]

In this study, the evolution of grain structures in Cu/Sn–3.5Ag/Cu– x Zn ( x =0 or 15 wt%) microbumps and SAC305/Cu– x Zn solder joints was investigated. Due to the small size of microbumps, impingement of interface IMCs easily occur. In a Cu/Sn–3.5Ag/Cu (wt%) microbump, the grain orientation of combined intermetallic compounds (IMCs) tends to be homogenous and closely-grouped, allowing cracks to more easily propagate. In order to examine the grain evolution of Cu–Sn IMCs, EBSD analysis was applied to microbumps and conventional-sized solder joints. Replacing the Cu substrate with Cu–Zn causes the grain orientation of Cu–Sn IMCs to become more random and dispersed, which may hinder crack propagation. It is thus expected that the reliability of Zn-doped microbumps and solder joints is superior to that of Cu substrate joints. [ABSTRACT FROM AUTHOR]

10 and 18 at. % copper incorporated NiO films were deposited by reactively sputtering from Ni targets covered with Cu strips of different sizes. A change in the valence of Ni from Ni2+ to Ni3+ is found by x-ray absorption near edge structure analysis after incorporating Cu into the films. All NiO films exhibit p-type conductivity, either without or with Cu additives. However, as compared with the pure NiO films, the carrier concentration of the films incorporating Cu increases, while the resistivity and mobility decrease. This study not only discusses the connections among the physical properties of the NiO films with different Cu contents but also clarifies the role of Cu additives in the NiO films. [ABSTRACT FROM AUTHOR]