A comparison of statistical methods for deriving freshwater quality criteria for the protection of aquatic organisms

Species sensitivity distributions (SSDs) are increasingly used in both ecological risk assessment and derivation of water quality criteria. However, there has been debate about the choice of an appropriate approach for derivation of water quality criteria based on SSDs because the various methods can generate different values. The objective of this study was to compare the differences among various methods. Data sets of acute toxicities of 12 substances to aquatic organisms, representing a range of classes with different modes of action, were studied. Nine typical statistical approaches, including parametric and nonparametric methods, were used to construct SSDs for 12 chemicals. Water quality criteria, expressed as hazardous concentration for 5 % of species (HC₅), were derived by use of several approaches. All approaches produced comparable results, and the data generated by the different approaches were significantly correlated. Variability among estimates of HC₅ of all inclusive species decreased with increasing sample size, and variability was similar among the statistical methods applied. Of the statistical methods selected, the bootstrap method represented the best-fitting model for all chemicals, while log-triangle and Weibull were the best models among the parametric methods evaluated. The bootstrap method was the primary choice to derive water quality criteria when data points are sufficient (more than 20). If the available data are few, all other methods should be constructed, and that which best describes the distribution of the data was selected.     

Characterization of the interactions between tetracycline antibiotics and microbial extracellular polymeric substances with spectroscopic approaches

The antibiotics have attracted global attentions for their impact on aquatic ecosystem. The knowledge about the fate of antibiotics encountering extracellular polymeric substances (EPS) is, however, limited. In this study, we investigated the interacting mechanisms of tetracycline (TC) to EPS extracted from aerobic activated sludge. The contributions of the main components of EPS, extracellular proteins, and polysaccharides were evaluated using bovine serum albumin and alginate sodium, respectively. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and nuclear magnetic resonance indicated that hydroxyl, carboxyl, and amino groups were the domain chemical groups involved in the interaction between TC and EPS, and the binding of TC onto EPS changed the structure of these chemical groups, thus causing shifts in their UV–visible absorption spectra. In addition, we found that extracellular proteins, rather than polysaccharides, were the major active contents involved in the interaction. Three-dimensional excitation–emission matrix fluorescence spectroscopy showed that the fluorophores in EPS were clearly quenched by TC and the static quenching process was observed, implying the complex formation of TC and EPS. Furthermore, thermodynamic analysis indicated that the binding of TC with EPS is spontaneous and dominated by electrostatic forces.     

汽油清净剂的研究应用及进展

随着环保要求的日趋严格及汽车工业的发展创新，开展汽油清净剂的研究和应用工作已势在必行。本文介绍了国内外汽油清净剂的发展过程、应用现状，同时还介绍了将清净分散剂、抗氧防腐剂、减磨剂、防锈剂等添加剂复合而成的汽油清净剂的研制情况。实验结果表明：该剂具有抑制和清除发动机燃燃油系统沉积物的性能，达到国外第三代同类产品的水平。     

Characterization of on-road vehicle emission factors and microenvironmental air quality in Beijing,China

In this paper, we report the results and analysis of a recent field campaign in August 2007 investigating the impacts of emissions from transportation on air quality and community concentrations in Beijing, China. We conducted measurements in three different environments, on-road, roadside and ambient. The carbon monoxide, black carbon and ultrafine particle number emission factors for on-road light-duty vehicles are derived to be 95 g kg^?1-fuel, 0.3 g kg^?1-fuel and 1.8 × 10¹⁵ particles kg^?1-fuel, respectively. The emission factors for on-road heavy-duty vehicles are 50 g kg^?1-fuel, 1.3 g kg^?1-fuel and 1.1 × 10¹⁶ particles kg^?1-fuel, respectively. The carbon monoxide emission factors from this study agree with those derived from remote sensing and on-board vehicle emission testing systems in China. The on-road black carbon and particle number emission factors for Chinese vehicles are reported for the first time in the literature. Strong traffic impacts can be observed from the concentrations measured in these different environments. Most clear is a reflection of diesel truck traffic activity in black carbon concentrations. The comparison of the particle size distributions measured at the three environments suggests that the traffic is a major source of ultrafine particles. A four-day traffic control experiment conducted by the Beijing Government as a pilot to test the effectiveness of proposed controls was found to be effective in reducing extreme concentrations that occurred at both on-road and ambient environments.     

Part V—sorption of pharmaceuticals and personal care products

Background, aim, and scope  Pharmaceuticals and personal care products (PPCPs) including antibiotics, endocrine-disrupting chemicals, and veterinary pharmaceuticals are emerging pollutants, and their environmental risk was not emphasized until a decade ago. These compounds have been reported to cause adverse impacts on wildlife and human. However, compared to the studies on hydrophobic organic contaminants (HOCs) whose sorption characteristics is reviewed in Part IV of this review series, information on PPCPs is very limited. Thus, a summary of recent research progress on PPCP sorption in soils or sediments is necessary to clarify research requirements and directions. Main features  We reviewed the research progress on PPCP sorption in soils or sediments highlighting PPCP sorption different from that of HOCs. Special function of humic substances (HSs) on PPCP behavior is summarized according to several features of PPCP–soil or sediment interaction. In addition, we discussed the behavior of xenobiotic chemicals in a three-phase system (dissolved organic matter (DOM)–mineral–water). The complexity of three-phase systems was also discussed. Results  Nonideal sorption of PPCPs in soils or sediments is generally reported, and PPCP sorption behavior is relatively a more complicated process compared to HOC sorption, such as the contribution of inorganic fractions, fast degradation and metabolite sorption, and species-specific sorption mechanism. Thus, mechanistic studies are urgently needed for a better understanding of their environmental risk and for pollution control. Discussion  Recent research progress on nonideal sorption has not been incorporated into fate modeling of xenobiotic chemicals. A major reason is the complexity of the three-phase system. First of all, lack of knowledge in describing DOM fractionation after adsorption by mineral particles is one of the major restrictions for an accurate prediction of xenobiotic chemical behavior in the presence of DOM. Secondly, no explicit mathematical relationship between HS chemical–physical properties, and their sorption characteristics has been proposed. Last but not least, nonlinear interactions could exponentially increase the complexity and uncertainties of environmental fate models for xenobiotics. Discussion on proper simplification of fate modeling in the framework of nonlinear interactions is still unavailable. Conclusions  Although the methodologies and concepts for studying HOC environmental fate could be adopted for PPCP study, their differences should be highly understood. Prediction of PPCP environmental behavior needs to combine contributions from various fractions of soils or sediments and the sorption of their metabolites and different species. Recommendations and perspectives  More detailed studies on PPCP sorption in separated soil or sediment fractions are needed in order to propose a model predicting PPCP sorption in soils or sediments based on soil or sediment properties. The information on sorption of PPCP metabolites and species and the competition between them is still not enough to be incorporated into any predictive models.     

Cation exchange in a glacial till drumlin at a road salt storage facility

At a former wood preservation plant severely contaminated with coal tar oil, in situ bulk attenuation and biodegradation rate constants for several monoaromatic (BTEX) and polyaromatic hydrocarbons (PAH) were determined using (1) classical first order decay models, (2) Michaelis–Menten degradation kinetics (MM), and (3) stable carbon isotopes, for o-xylene and naphthalene. The first order bulk attenuation rate constant for o-xylene was calculated to be 0.0025 d^− 1 and a novel stable isotope-based first order model, which also accounted for the respective redox conditions, resulted in a slightly smaller biodegradation rate constant of 0.0019 d^− 1. Based on MM-kinetics, the o-xylene concentration decreased with a maximum rate of k_max = 0.1 µg/L/d. The bulk attenuation rate constant of naphthalene retrieved from the classical first order decay model was 0.0038 d^− 1. The stable isotope-based biodegradation rate constant of 0.0027 d^− 1 was smaller in the reduced zone, while residual naphthalene in the oxic part of the plume further downgradient was degraded at a higher rate of 0.0038 d^− 1. With MM-kinetics a maximum degradation rate of k_max = 12 µg/L/d was determined. Although best fits were obtained by MM-kinetics, we consider the carbon stable isotope-based approach more appropriate as it is specific for biodegradation (not overall attenuation) and at the same time accounts for the dominant electron-accepting process. For o-xylene a field based isotope enrichment factor ε_field of − 1.4 could be determined using the Rayleigh model, which closely matched values from laboratory studies of o-xylene degradation under sulfate-reducing conditions.     

Cosorption of organic chemicals with different properties: their shared and different sorption sites

Complementary sorption of different chemicals was expected and investigating the relationship between the sorption inhibition of primary sorbate (ΔQ(pri)) and sorption of secondary sorbate (Q(sec)) could provide a new angle to understand coadsorption of different chemicals. This study used bisphenol A (BPA) as the primary adsorbate, sulfamethoxazole (SMX) as the competitor, and carbon nanotubes as model adsorbents to study their complementary and competitive adsorption. At low BPA concentrations, the sorption of SMX (Q(sec)) exceeded BPA sorption inhibition (ΔQ(pri)), indicating that these two chemicals complementarily adsorbed on their respectively preferred sorption sites. At high BPA concentrations, higher ΔQ(pri) was observed in comparison to Q(sec), which may be resulted from different packing efficiencies of the adsorbed SMX and BPA. This study emphasized that both competitive and complementary sorption should be discussed in binary sorption system.     

Binding of polycyclic aromatic hydrocarbons by humic acids formed during composting

Binding of two model polycyclic aromatic hydrocarbons (PAHs), phenanthrene and pyrene, by humic acids (HAs) isolated from an organic substrate at different stages of composting and a soil was investigated using a batch fluorescence quenching method and the modified Freundlich model. With respect to soil HA, the organic substrate HA fractions were characterized by larger binding affinities for both phenanthrene and pyrene. Further, isotherm deviation from linearity was larger for soil HA than for organic substrate HAs, indicating a larger heterogeneity of binding sites in the former. The composting process decreased the binding affinity and increased the heterogeneity of binding sites of HAs. The changes undergone by the HA fraction during composting may be expected to contribute to facilitate microbial accessibility to PAHs. The results obtained also suggest that bioremediation of PAH-contaminated soils with matured compost, rather than with fresh organic amendments, may result in faster and more effective cleanup.     

Detection of DDT and its metabolites in two estuaries of South China using a SPME-based device: First report of p,p′-DDMU in water column

A solid-phase microextration-based sampling method was employed to determine the concentrations of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) and its metabolites, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (DDD), 1,1-dichloro-2,2-bis(p-chlorophenyl)ethene (DDE) and 1-chloro-2,2-bis(p-chlorophenyl)ethene (DDMU), in two estuarine bays, Daya Bay and Hailing Bay, of South China. Six DDT components including p,p′-DDT, o,p′-DDD, p,p′-DDD, o,p′-DDE, p,p′-DDE, and p,p′-DDMU were detected in Hailing Bay, while only p,p′-DDD was found in Daya Bay. p,p′-DDD was the most abundant DDT component in both bays, sharply different from the previous finding in the water column of the Palos Verdes Shelf, California, USA that p,p′-DDE was prevalent. In addition, the occurrence of p,p′-DDMU (with a range of 0.047-0.21 ng/L in Hailing Bay) has not been reported around the globe, and its presence in our study region appeared to stem from dehydrochlorination of p,p′-DDD, favored under aerobic conditions, but further investigations are clearly needed to confirm the mechanism for generation of DDMU in estuarine environments.     

Sorption of organic contaminants by biopolymers: role of polarity, structure and domain spatial arrangement

Sorption behavior of hydrophobic organic contaminants (HOCs) (i.e., pyrene, phenanthrene and naphthalene) by native and chemically modified biopolymers (lignin, chitin and cellulose) was examined. Lignins (native and treated) showed nonlinear sorption for all compounds studied, emphasizing their glassy character. Chitins and celluloses had linear isotherms for phenanthrene and naphthalene, illustrating the dominance of partitioning, while pyrene yielded nonlinear isotherms. Sorption capacity (K(oc)) of HOCs was negatively correlated with the polarity [(O+N)/C] of the biopolymers. Aromatic and alkyl+aromatic C percentages, rather than alkyl C content, demonstrated a better correlation with K(oc) values, indicating the importance of aromatic structures for HOC affinity. Hydrophobicity (K(ow))-normalized K(oc) values decreased sharply with increasing percentage of O-alkyl C versus total aliphatic C (O-alkyl C/total aliphatic C) or with polar C/(alkyl+aromatic C) ratio of the biopolymers until their values reached 80% and 4, respectively, illustrating the effect of surrounding polar groups on reducing affinity for HOCs. Overall, the results of this study highlight the role of spatial arrangement of domains within biopolymers in sorption of HOCs, and point to sorbent properties, such as functionality, polarity and structure, jointly regulating the sorption of HOCs in biopolymers.