Yunsong Mu

Removal of Phosphate from Eutrophic Lakes through Adsorption by in Situ Formation of Magnesium Hydroxide from Diatomite

Since in situ formation of Mg(OH)2 can efficiently sorb phosphate (PO4) from low concentrations in the environment, a novel dispersed magnesium oxide nanoflake-modified diatomite adsorbent (MOD) was developed for use in restoration of eutrophic lakes by removal of excess PO4. Various adsorption conditions, such as pH, temperature and contact time were investigated. Overall, sorption capacities increased with increasing temperature and contact time, and decreased with increasing pH. Adsorption of PO4 was well described by both the Langmuir isotherm and pseudo second-order models. Theoretical maximum sorption capacity of MOD for PO4 was 44.44-52.08 mg/g at experimental conditions. Characterization of PO4 adsorbed to MOD by use of X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and solid state (31)P nuclear magnetic resonance revealed that electrostatic attraction, surface complexation and chemical conversion in situ were the major forces in adsorption of PO4. Mg(OH)2 formed in situ had a net positive charge on the surface of the MOD that could adsorb PO4(3-) and HPO4(2-) anion to form surface complex and gradually convert to Mg3(PO4)2 and MgHPO4. Efficiency of removal of PO4 was 90% when 300 mg MOD/L was added to eutrophic lake water. Results presented here demonstrated the potential use of the MOD for restoration of eutrophic lakes by removal of excess PO4.

Predicting Water Quality Criteria for Protecting Aquatic Life from Physicochemical Properties of Metals or Metalloids

Metals are widely distributed pollutants in water and can have detrimental effects on some aquatic life and humans. Over the past few decades, the United States Environmental Protection Agency (U.S. EPA) has published a series of criteria guidelines, which contain specific criteria maximum concentrations (CMCs) for 10 metals. However, CMCs for other metals are still lacking because of financial, practical, or ethical restrictions on toxicity testing. Herein, a quantitative structure activity relationship (QSAR) method was used to develop a set of predictive relationships, based on physical and chemical characteristics of metals, and predict acute toxicities of each species for five phyla and eight families of organisms for 25 metals or metalloids. In addition, species sensitivity distributions (SSDs) were developed as independent methods for determining predictive CMCs. The quantitative ion character-activity relationships (QICAR) analysis showed that the softness index (σp), maximum complex stability constants (log -β(n)), electrochemical potential (ΔE(0)), and covalent index (X(m)(2)r) were the minimum set of structure parameters required to predict toxicity of metals to eight families of representative organisms. Predicted CMCs for 10 metals are in reasonable agreement with those recommended previously by U.S. EPA within a difference of 1.5 orders of magnitude. CMCs were significantly related to σp (r(2) = 0.76, P = 7.02 × 10(-9)) and log -β(n) (r(2) = 0.73, P = 3.88 × 10(-8)). The novel QICAR-SSD model reported here is a rapid, cost-effective, and reasonably accurate method, which can provide a beneficial supplement to existing methodologies for developing preliminarily screen level toxicities or criteria for metals, for which little or no relevant information on the toxicity to particular classes of aquatic organisms exists.

Anti-androgen activity of polybrominated diphenyl ethers determined by comparative molecular similarity indices and molecular docking.

Some polybrominated diphenyl ethers (PBDEs) may have endocrine-disrupting (ED) potencies. In this study, molecular docking and three-dimensional quantitative structure-activity relationship (3D-QSAR) were performed to explore the possible anti-androgenicity of PBDEs. Based on the alignment generated by docking conformations, a highly predictive comparative molecular similarity indices analysis (CoMSIA) model was developed with q(2) value of 0.642 and r(2) value of 0.973. The contributions of the steric, electrostatic, hydrophobic fields to the CoMSIA model are 13.1%, 61.0% and 25.9%, respectively. Br substitutions which are at meta and para positions of PBDEs will be unfavorable for androgen receptor (AR) antagonism and ortho Br substitutions for PBDEs are favorable for anti-androgen activity. Mapping the 3D-QSAR models to the active site of the AR provides new insight into the AR-PBDEs interaction. CoMSIA field contributions showed good consistency with structural features of the AR binding site and can be used to predict anti-androgen activities of other PBDE congeners.

Predicting toxic potencies of metal oxide nanoparticles by means of nano-QSARs

Abstract Background: The enormous physicochemical and structural diversity of metal oxide nanoparticles (MeONPs) poses significant challenges to the testing of their biological uptake, biodistribution, and effects that can be used to develop understanding of key nano-bio modes of action. This has generated considerable uncertainties in the assessment of their human health and environmental risks and has raised concerns about the adequacy of their regulation. In order to surpass the extremely resource intensive case-by-case testing, intelligent strategies combining testing methods and non-testing predictive modeling should be developed. Methods: The quantitative structure-activity relationship (QSARs) in silico tools can be instrumental in understanding properties that affect the potencies of MeONPs and in predicting toxic responses and thresholds of effects. Results: The present study proposes a predictive nano-QSAR model for predicting the cytotoxicity of MeONPs. The model was applied to test the relationships between 26 physicochemical properties of 51 MeONPs and their cytotoxic effects in Escherichia coli. The two parameters, enthalpy of formation of a gaseous cation (▵Hme+) and polarization force (Z/r), were elucidated to make a significant contribution for the toxic effect of these MeONPs. The study also proposed the mechanisms of toxic potency in E. coli through the model, which indicated that the MeONPs as well as their released metal ions could collectively induce DNA damage and cell apoptosis. Significance: These findings may provide an alternative method for prioritizing current and future MeONPs for potential in vivo testing, virtual prescreening and for designing environmentally benign nanomaterials.

Predicting criteria continuous concentrations of 34 metals or metalloids by use of quantitative ion character-activity relationships-species sensitivity distributions (QICAR-SSD) model.

Criteria continuous concentrations (CCCs) are useful for describing chronic exposure to pollutants and setting water quality standards to protect aquatic life. However, because of financial, practical, or ethical restrictions on toxicity testing, few data are available to derive CCCs. In this study, CCCs for 34 metals or metalloids were derived using quantitative ion character-activity relationships-species sensitivity distributions (QICAR-SSD) and the final acute-chronic ratio (FACR) method. The results showed that chronic toxic potencies were correlated with several physico-chemical properties among eight species chosen, where the softness index was the most predictive characteristic. Predicted CCCs for most of the metals, except for Lead and Iron, were within a range of 10-fold of values recommended by the U.S. EPA. The QICAR-SSD model was superior to the FACR method for prediction of data-poor metals. This would have significance for predicting toxic potencies and criteria thresholds of more metals or metalloids.

Derivation of marine water quality criteria for metals based on a novel QICAR-SSD model

Establishment of water quality criteria (WQC) is one procedure for protection of marine organisms and their ecosystems. This study, which integrated two separate approaches, quantitative ion character–activity relationships (QICARs) and species sensitivity distributions (SSDs), developed a novel QICAR-SSD model. The QICARs predict relative potencies of individual elements while SSDs integrate relative sensitivities among organisms. The QICAR-SSD approach was applied to derive saltwater WQC for 34 metals or metalloids. Relationships between physicochemical properties of metal ions and their corresponding potencies for acute toxicity to eight selected marine species were determined. The softness index (σp) exhibited the strongest correlation with the acute toxicity of metals (r2 > 0.66, F > 5.88, P < 0.94 × 10−2). Predictive criteria maximum concentrations for the eight metals, derived by applying the SSD approach to values predicted by use of QICARs, were within the same order of magnitude as values recommended by the US EPA (2009). In general, the results support that the QICAR-SSD approach is a rapid method to estimate WQC for metals for which little or no information is available for marine organisms.

Setting water quality criteria in China: approaches for developing species sensitivity distributions for metals and metalloids.

Both nonparametric and parametric approaches were used to construct SSDs for use in ecological risk assessments. Based on toxicity to representative aquatic species and typical water contaminants of metals and metalloids in China, nonparametric methods based on the bootstrap were statistically superior to the parametric curve-fitting approaches. Knowing what the SSDs for each targeted species are might help in selecting efficient indicator species to use for water quality monitoring. The species evaluated herein showed sensitivity variations to different chemical treatments that were used in constructing the SSDs. For example, D. magna was more sensitive than most species to most chemical treatments, whereas D. rerio was sensitive to Hg and Pb but was tolerant to Zn. HC5 values, derived for the pollutants in this study for protecting Chinese species, differed from those published by the USEPA. Such differences may result from differences in geographical conditions and biota between China and the United States. Thus, the degree of protection desired for aquatic organisms should be formulated to fit local conditions. For approach selection, we recommend all approaches be considered and the most suitable approaches chosen. The selection should be based on the practical information needs of the researcher (viz., species composition, species sensitivity, and geological characteristics of aquatic habitats), since risk assessments usually are focused on certain substances, species, or monitoring sites. We used Tai Lake as a typical freshwater lake in China to assess the risk of metals and metalloids to the aquatic species. We calculated hazard quotients for the metals and metalloids that were found in the water of this lake. Results indicated the decreasing ecological risk of these contaminants in the following order: Hg <As<Ni<Zn<Cu<Cd<Pb<Cr. From the methodological perspective, six SSD approaches used delivered different WQC values and affected the risk assessment results of the metals and metalloids to aquatic species. Based on the MEC and HC5 derived from SSDs by nonparametric and parametric approaches together, the risk levels of metals and metalloids were characterized from their hazard quotients as being high risk (Cr, Pb, Cd, and Cu), medium risk (Zn and Ni), or low risk (As and Hg).

Toxicity Reference Values for Protecting Aquatic Birds in China from the Effects of Polychlorinated Biphenyls

PCBs are typical of persistent, bioaccumulative and toxic compounds (PBTs) that are widely distributed in the environment and can biomagnify through aquatic food webs, because of their stability and lipophilic properties. Fish-eating birds are top predators in the aquatic food chain and may suffer adverse effects from exposure to PCB concentrations. In this review, we address the toxicity of PCBs to birds and have derived tissue residue guidelines (TRGs) and toxic reference values (TRVs) for PCBs for protecting birds in China. In deriving these protective indices, we utilized available data and three approaches, to wit: species sensitivity distribution (SSD), critical study approach (CSA) and toxicity percentile rank method (TPRM). The TRGs and TRVs arrived at by using these methods were 42.3, I 0. 7, 4.3 pg TEQs/g diet wm and 16.7, 15.5, and 5.5 pg TEQs/g tissue wm for the CSA SSD and TPRM approaches, respectively. These criteria values were analyzed and compared with those derived by others. The following TRG and TRY, derived by SSD, were recommended as avian criteria for protecting avian species in China: 10.7 pg TEQs/g diet wm and 15.5 pg TEQs/g tissue wm, respectively. The hazard of PCBs to birds was assessed by comparing the TRVs and TRGs derived in this study with actual PCB concentrations detected in birds or fish. The criteria values derived in this study can be used to evaluate the risk of PCBs to birds in China, and to provide indices that are more reasonable for protecting Chinese avian species. However, several sources of uncertainty exists when deriving TRGs and TRVs for the PCBs in birds, such as lack of adequate toxicity data for birds and need to use uncertainty factors. Clearly, relevant work on PCBs and birds in China are needed in the future. For example, PCB toxicity data for resident avian species in China are needed. In addition, studies are needed on the actual PCB levels in birds and fish in China. Such information is needed to serve as a more firm foundation for future risk assessments.

Directly Predicting Water Quality Criteria from Physicochemical Properties of Transition Metals

Transition metals are a group of elements widespread in aquatic environments that can be hazardous when concentrations exceeding threshold values. Due to insufficient data, criteria maximum concentrations (CMCs) of only seven transition metals for protecting aquatic life have been recommended by the USEPA. Hence, it is deemed necessary to develop empirical models for predicting the threshold values of water quality criteria (WQC) for other transition metals for which insufficient information on toxic potency is available. The present study established quantitative relationships between recommended CMCs and physicochemical parameters of seven transition metals, then used the developed relationships to predict CMCs for other transition metals. Seven of 26 physicochemical parameters examined were significantly correlated with the recommended CMCs. Based on this, five of the seven parameters were selected to construct a linear free energy model for predicting CMCs. The most relevant parameters were identified through principle component analysis, and the one with the best correlation with the recommended CMCs was a combination of covalent radius, ionic radius and electron density. Predicted values were largely consistent with their toxic potency values. The present study provides an alternative approach to develop screening threshold level for metals which have insufficient information to use traditional methods.

Interspecies Correlation Estimation–Applications in Water Quality Criteria and Ecological Risk Assessment

Criteria and Ecological Risk Assessment Chenglian Feng,† Fengchang Wu,*,† Yunsong Mu,† Wei Meng,† Scott D. Dyer,‡ Ming Fan,‡ Sandy Raimondo, and Mace G. Barron †State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China ‡The Procter & Gamble Company, Global Product Stewardship, Mason Business Center, Mason, Ohio 45040, United States United States Environmental Protection Agency, Gulf Ecology Division, Gulf Breeze, Florida 32561, United States