Inconsistency and comprehensiveness of risk assessments for heavy metals in urban surface sediments

Numerous indices have been developed to assess environmental risk of heavy metals in surface sediments, including the total content based geoaccumulation index (I_geo), exchangeable fraction based risk assessment code (RAC), and biological toxicity test based sediment quality guidelines (SQGs). In this study, the three indices were applied to freshwater surface sediments from 10 sections along an urbanization gradient of the Grand Canal, China to assess the environmental risks of heavy metals (Cu, Pb, Zn, Cd, and Cr) and to understand discrepancies of risk assessment indices and urbanization effects regarding heavy metal contamination. Results showed that Cd, Zn, and Pb were the most enriched metals in urban sections assessed by I_geo and over 95% of the samples exceeded the Zn and Pb thresholds of the effect range low (ERL) of SQGs. According to RAC, Cu, Zn, Cd, and Cr had high risks of adversely affecting the water quality of the Grand Canal due to their remarkable portions of exchangeable fraction in surface sediment. However, Pb showed a relative low risk, and was largely bounded to Fe/Mn oxides in the urban surface sediments. Obviously, the three assessment indices were not consistent with each other in terms of predicting environmental risks attributed to heavy metals in the freshwater surface sediments of this study. It is recommended that risk assessment by SQGs should be revised according to availability and site specificity. However, the combination of the three indices gave us a comprehensive understanding of heavy metal risks in the urban surface sediments of the Grand Canal.     

Cu fractions, mobility and bioavailability in soil-wheat system after Cu-enriched livestock manure applications

Fertilization of crops with livestock manure (LM) is a common waste disposal option, but repeated application of LM containing high concentrations of heavy metals such as Cu could lead to crop toxicity and environmental risk. To examine the Cu availability and uptake by wheat in a Mollisol affected by Cu-enriched LM, pot experiments were conducted. LM (376 mg kg⁻¹ Cu originally) was spiked with different concentrations of Cu (0, 100, 200, 400, 600 and 800 mg kg⁻¹ soil, added as CuSO₄) to simulate soil Cu contamination by LM application. The results indicated that Cu was predominately distributed in organic bound fraction, while the most drastic increase was found in reducible fraction. Acid-extractable fraction played a more important role than other fractions in controlling the mobility and bioavailability of Cu. DTPA-extractable Cu may overestimate the Cu bioavailability since DTPA solution could extract soluble and part of stable forms. The application of LM at 1% level significantly decline the Cu mobility, but that at 3% level exhibited the opposite effect.Although the quantities of Cu in wheat was very low compared with the accumulation in soil, Cu concentrations in roots increased evidently from 12 to 533 mg kg⁻¹ and that in aerial parts were in a narrow range from 12.1 to 32.7 mg kg⁻¹, indicating the more sensitivity of roots to the Cu toxicity. The Cu concentrations in grains after 3% manure application did not approach the threshold for Cu toxicity (<20 mg kg⁻¹) even at higher Cu addition rates.     

Analysis of surface and aerosol polarized reflectance for aerosol retrievals from polarized remote sensing in PRD urban region

A precise estimate of polarization induced by surface is crucial for polarized remote sensing dedicated to monitoring aerosol properties over urban area. The accurate knowledge of interaction between surface and aerosol polarized reflectance is essential for accurately achieving aerosol properties. In order to study surface and aerosol polarized reflectance for aerosol retrievals over urban area, a new airborne directional polarimetric camera (DPC) with high spatial resolution (4 m at 4000 m a.g.l) was developed. The surface polarized reflectance over distinct surface covers of urban area (forest, shrub, and soil) were studied using DPC measurements during a field campaign in the Pearl River Delta (PRD), China. The large variations were found in surface polarized reflectance of distinct urban covers due to surface type variability. For all surface types, the empirical BPDF model cannot describe accurately surface polarized reflectance at all possible illumination and observation geometries. From the quantitatively study of relationship between surface and aerosol polarized contribution to DPC measurements, we show that the polarized contributions of aerosol, which optical properties were defined by ground-based measurements, are much larger than the polarized contribution of surface, and found that the polarized contribution of surface covers increases with decreasing NDVI. The effect of polarization accuracy of measurements on aerosol retrieval was also investigated using DPC measurements, and found that 0.1% polarization accuracy of measurements can be neglected when AOD is retrieved using polarized measurements. Based on the information of effects of polarized reflectance differences between distinct surface covers and polarization accuracy of polarized measurements on retrieved aerosols over urban area, we found that the accuracy of aerosol retrieval over forest covers is higher than other surface types using polarized remote sensing.     

Rapid incorporation and short-term distribution of a nonylphenol isomer and the herbicide MCPA in soil-derived organo-clay complexes

Organo-clay complexes in soil are a major sink for xenobiotics and, thus, often enhance their persistence dramatically. However, the knowledge on environmental processes of non-extractable residue formation on a short time scale is very restricted. Therefore, this study examined the distribution of 4-(3,5-dimethylhept-3-yl)phenol (NP) and 4-chloro-2-methylphenoxyacetic acid (MCPA) in soil over a short time period of 48 h and in different soil sub-fractions. The overall proportion of organo-clay-associated bound residues was not only abundant but also in the same range for both substances (MCPA: 8%; NP: 11% of applied ¹⁴C-radioactivity). However, a more detailed view revealed two different distribution patterns: a higher proportion of clay-associated NP was accompanied by a lower content of bound residues, whereas a smaller fraction of clay-associated MCPA was characterized by a higher proportion of non-extractable residues. Further on, a selective accumulation of bound residues among clay-associated humic fractions was observed. NP residues were linked predominantly to humic acids, whereas MCPA residues tended to be incorporated more into fulvic acids. It was evident that the overall distribution was influenced primarily by the physico-chemical properties of the contaminants. This study demonstrates in detail a rapid initial incorporation accompanied by a specific distribution into soil sub-fractions for selected xenobiotics in soil and points to a complex interaction of clay-associated organic matter with low molecular weight compounds.     

Removal of arsenic from aqueous solution by two types of nano TiO2 crystals

Titanium dioxide (TiO₂) is a promising sorbent for As removal. There are two main and physico-chemically distinct polymorphs of TiO₂ in nature, namely anatase and rutile. Since the difference of arsenic removal by the two polymorphs of TiO₂ is now well known, study on the arsenic removal efficiency and the underlying mechanism is of great significance in developing new remediation strategies for As-polluted waters. Here batch experiments were carried out in combination with instrumental analysis of X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) to investigate the effects, influential factors and mechanisms of As removal from aqueous solution by two types of nano TiO₂ crystals. The adsorption behavior of anatase and rutile for As(V) and As(III) are well described by Freundlich equations. Anatase had higher As removal efficiency and adsorption capacity than rutile. Solution pH had no influence on the As adsorption of anatase TiO₂, whereas the As removal by rutile TiO₂ was increased by 7?C18% with pH from 4 to 10. Presence of accompanying anions such as phosphate, silicate, nitrate and sulfate, decreased the As(V) and As(III) removal by both crystals, with phosphate being the most effective. However, removal of As by rutile TiO₂ was greatly enhanced in the presence of divalent cations i.e. Ca²⁺ and Mg²⁺. Shading of light decreased the removal of As(V) and As(III) of anatase by 15.5% and 17.5%, respectively, while a slight increase of As removal was observed in the case of Rutile TiO₂. FT-IR characterization of As(V) or As(III)-treated nano TiO₂ crystals indicated that both Ti-O and As-O groups participated in As adsorption. Both FT-IR and XPS analysis demonstrated that As(III) was photooxidated into As(V) when adsorbed by anatase under the light condition. Thus, the effect of crystal types and light condition on As removal should be taken into consideration when nano TiO₂ is applied for As removal from water.     

Mobility of acid-treated carbon nanotubes in water-saturated porous media

The production, use, and disposal of nanomaterials may inevitably lead to their appearance in water. With the development of new industries around nanomaterials, it seems necessary to be concerned about the transport of nanomaterials in the environment. In this paper, the transport of acid-treated carbon nanotubes (CNTs) in porous media was investigated. Before the mobility investigation, the stability of acid-treated CNT dispersions was studied using ultraviolet-visible spectra and it was indicated that, under the chemical conditions employed in this work, there was no apparent aggregation. The mobility investigation showed that transport of acid-treated CNTs increased with treatment time due to increase in particle zeta potential. Carbon nanotubes treated with nitric acid for 2, 6, and 12 h possessed measured zeta potentials of -30.0, -43.0, and -48.5 mV, respectively. Utilizing clean-bed filtration theory, we showed that acid-treated CNTs have the potential to migrate 3.28, 5.67, and 7.69 m in saturated glass beads, respectively. We showed that solution ionic strength and pH have important effects on the mobility of acid-treated CNTs. Increasing the pH from 6.0 to 7.9 resulted in an increase in migration potential from 2.96 to 10.86 m. Increasing the ionic strength from 0.005 to 0.020 M resulted in a decrease in CNT migration potential from 5.67 to 1.42 m.     

Emergy evaluation and economic analysis of three wetland fish farming systems in Nansi Lake area,China

Emergy and economic methods were used to evaluate and compare three fish production models, i.e., cage fish farming system, pond intensive fish rearing system and semi-natural extensive pond fish rearing system, in Nansi Lake area in China in the year 2007. The goal of this study was to understand the benefits and driving forces of selected fish production models from ecological and economic points of view. The study considered input structure, production efficiency, environmental impacts, economic viability and sustainability. Results show that the main difference among the three production systems was the emergy cost for fish feed associated with their feeding system, i.e., feeding on natural biomass such as plankton and grass or on commercial feedstock. As indicated by EYR, ELR and ESI, it can be clearly shown that the intensive production model with commercial feed is not a sustainable pattern. However, the point is that more environmentally sound patterns do not seem able to provide a competitive net profit in the short run. The intensive pond fish farming system had a net profit of 2.57E+03 $/ha, much higher than 1.27E+03 $/ha for cage fish farming system and slightly higher than 2.37E+03 $/ha for semi-natural fish farming system. With regard to the drivers of local farmer’s decisions, the accessibility of land for the required use and investment ability determine the farmer’s choice of the production model and the scale of operation, while other factors seem to have little effect. Theoretically, the development of environmentally sustainable production patterns, namely water and land conservation measures, greener feed as well as low waste systems is urgently needed, to keep production activities within the carrying capacity of ecosystems. Coupled emergy and economic analyses can provide better insight into the environmental and economic benefits of fish production systems and help solve the problems encountered during policy making.     

ELISA detection of multixenobiotic resistance transporter induction in indigenous freshwater Chironomidae larvae (Diptera): A biomarker calibration step for in situ monitoring of xenobiotic exposure

A new simple and sensitive method to distinguish chemically polluted from unpolluted situations in freshwater ecosystems is reported. For this purpose, Chironomus gr thumni larvae were collected from a polluted urban river downstream a sewage treatment plant. For the first time, ELISA assay was used to semi-quantify the multixenobiotic resistance transporters (MXR) in these small pertinent bioindicators. The use of samples immediately fixed in the field gives a delay to isolate larvae and allows multi-sampling along a longitudinal transect in a river at a given time. Results exhibit an induction of MXR proteins in larvae from the polluted river and a deinduction in larvae maintained 11days in unpolluted water. They show new evidences to use midge larvae in biomonitoring environmental programs. They answer to first biomarker calibration steps for the ongoing development of MXR transporters as a detection tool of xenobiotic impacts on bioindicator invertebrates in their freshwater habitats.     

Study of the use of coal fly ash as an additive to minimise fluoride leaching from FGD gypsum for its disposal

The use of coal fly ash as a fluoride retention additive has been studied as a way of treating flue gas desulphurisation (FGD) gypsum for its disposal in landfills. With this end leaching studies following the standard EN-12457-4 [Characterization of waste- Leaching-Compliance test for leaching of granular waste materials and sludges - Part 4: One stage batch test at a liquid to solid ratio of 10l/kg for materials with particle size below 10mm (without or with size reduction)] have been performed on FGD gypsum samples treated with different proportions of fly ash (0.1-100%). It was found that the fluoride leachable content in FGD gypsum was reduced in the range 1-55%, depending on the fly ash proportion added to FGD gypsum. High levels of fluoride leaching reduction (close to 40%) were achieved even at relatively low fly ash additions (5%). So, low fly ash incorporations assure the characterization of this by-product as a waste acceptable at landfills for non-hazardous wastes according to the Council Decision 2003/33/EC [Council Decision 2003/33/EC of 19 December 2002 establishing criteria and procedures for the acceptance of waste at landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC] on waste disposal. Furthermore, the effectiveness of the proposed FGD gypsum stabilization method was also studied in column leaching systems, proving its good performance in simulated conditions of disposal. In such conditions a fluoride leaching reduction value slightly higher than 25% was displayed for a fly ash added amount of 5%.