Toluene-mercuric modified USEPA Method 3060A to eliminate interference of sulfide-based reductants with Cr(VI) determination.

The validity of USEPA Method 3060A as universal Cr(VI) analysis method for remediated soil is controversial. We investigated soil Cr(VI) remediation performance by commonly used reductants (FeSO4, CaSx, Na2S) under different operating conditions (dosage, curing time and degree of mixing) using Method 3060A, and developed modified 3060A specific for sulfide-based reductants. Results showed that Cr(VI) was primarily removed during analysis stage rather than remediation stage. Thereinto, chemical dosage played a much more important role than curing time and degree of mixing. Besides, soil Cr(VI) concentration decreased to below the detection limit with residual reductant content increasing. Comparing standard and toluene-mercuric modified 3060A, Cr(VI) removal efficiency decreased from 100 % to 38.9-45.4 %, 67.1-68.8 % and 94.1-96.3 %, corresponding to mixing degree of 33 %, 67 % and 100 %, for treated soil using 1× and 2× the molar stoichiometric ratio of CaSx. Subsequently, the optimization mechanism was revealed. Elemental sulfur, remediation product of sulfide-based reductants, was removed from soil by toluene preventing its disproportionation to sulfide at Method 3060A stage. Sulfide was fixed by mercuric oxide in species of mercuric sulfide. This method also proved suitable for different types of soils. Therefore, an effective way for scientific evaluation of soil Cr(VI) remediation was provided in this study.

Overestimate of remediation efficiency due to residual sodium persulfate in PAHs contaminated soil and a solution.

Oxidation remediation is a commonly used technology for PAHs contaminated soil presently, but the overestimate of efficiency due to ongoing remediation by residual oxidants during extraction and testing has not been paid enough attention. In this study, persulfate was activated by Fe(II) to investigate the effects of residual oxidants on PAHs removal during detection process and the elimination effects of adding Na2SO3 and extending sampling time on residual oxidants. Results verified that the residual oxidants removed PAHs in extraction process, making the results lower than the actual values: the detection recovery rate η of ∑PAHs and 3-6 ring PAHs ranged from 24.3% (25% Na2S2O8 treatment) to 87.4% (5% Na2S2O8+4/4Fe2+ treatment), 20.1%-99.0%, 28.9%-87.9%, 20.8%-89.4%, and 18.6%-76.9%, respectively. After adding Na2SO3, the accuracy of detection results increased significantly: the η of ∑PAHs and 3-6 ring PAHs increased to 64.1%-96.5%, 58.8%-95.5%, 73.8%-114.4%, 60.6%-95.6%, and 45.4%-77.1%, respectively. After 49 days of adding oxidants, residual oxidants had no considerable effect on the detection of PAHs, indicating it was appropriate to start soil remediation verification sampling49 days after the remediation was completed. The observed results will help scientific evaluation of the remediation effects of chemical oxidation on organic contaminated soil.

Translocation and biotransformation of CuO nanoparticles in rice (Oryza sativa L.) plants.

Metal-based nanoparticles (MNPs) may be translocated and biochemically modified in vivo, which may influence the fate of MNPs in the environment. Here, synchrotron-based techniques were used to investigate the behavior of CuO NPs in rice plants exposed to 100 mg/L CuO NPs for 14 days. Micro X-ray fluorescence (µ-XRF) and micro X-ray absorption near edge structure (µ-XANES) analysis revealed that CuO NPs moved into the root epidermis, exodermis, and cortex, and they ultimately reached the endodermis but could not easily pass the Casparian strip; however, the formation of lateral roots provided a potential pathway for MNPs to enter the stele. Moreover, bulk-XANES data showed that CuO NPs were transported from the roots to the leaves, and that Cu (II) combined with cysteine, citrate, and phosphate ligands and was even reduced to Cu (I). CuO NPs and Cu-citrate were observed in the root cells using soft X-ray scanning transmission microscopy (STXM).

Phytotoxicity and accumulation of copper oxide nanoparticles to the Cu-tolerant plant Elsholtzia splendens.

The release of nanoparticles (NPs) to the environment poses an increasing potential threat to biological systems. This study investigated the phytotoxicity and accumulation of copper oxide (CuO) NPs to Elsholtzia splendens (a Cu-tolerant plant) under hydroponic conditions. The 50% effective concentration (EC50) of CuO NPs to E. splendens was about 480 mg/L, implying the tolerance of E. splendens to CuO NPs. The Cu content in the shoots treated with 1000 mg/L CuO NPs was much higher than those exposed to the comparable 0.5 mg/L soluble Cu and CuO bulk particles. CuO NPs-like deposits were found in the root cells and leaf cells. Cu K-edge X-ray absorption near-edge structure analysis further revealed that the accumulated Cu species existed predominantly as CuO NPs in the plant tissues. All these results suggested that CuO NPs can be absorbed by the roots and translocated to the shoots in E. splendens.

Differences in soil properties and bacterial communities between the rhizosphere and bulk soil and among different production areas of the medicinal plant Fritillaria thunbergii.

To explore rhizosphere effects, geographical differences and their effects on the bacterial community associated with the geoherb Fritillaria thunbergii, some physicochemical properties of soil samples (3 sampling sites × 2 habitats (rhizosphere and bulk soil)) were measured and the soil bacterial community detected by PCR-denaturing gradient gel electrophoresis (DGGE). Among the three regions, soil pH varied between 4.48 and 7.73 indicating that F. thunbergii could grow both in acid and slightly alkaline soil. As the authentic Dao-di producing area, Ningbo showed the highest soil quality with the highest content of organic matter (OM) (2.46%), phosphatase (268 mg kg(-1) 24 h(-1)) and urease activity (1481 mg kg(-1) 24 h(-1)). In comparison with the bulk soil, pH, organic carbon content, and phosphatase and urease activities were all lower in the rhizosphere, suggesting that the roots may secrete some unique metabolites in root exudates. Statistical analyses showed that soil properties of Ningbo and Panan in Zhejiang province were more similar to each other than those in Nantong in Jiangsu province. In addition, PCR-DGGE analysis showed that main bacterial population identified in F. thunbergii was proteobacteria (18 bands, 55%), acidobacteria (4, 12%), actinobacteria (4, 12%) and bacterioidetes (6, 18%). Overall, soil properties and microbial communities varied not only between the rhizosphere and bulk soil but also among the three regions. We suggest that the plant, together with the soil properties, cooperatively shape the structure of the rhizosphere bacteria, and that the soil properties have a close relationship with the geoherbalism of F. thunbergii.

Sorption and distribution of copper in unsaturated Pseudomonas putida CZ1 biofilms as determined by X-ray fluorescence microscopy.

The spatial and temporal distribution of metals in unsaturated Pseudomonas putida CZ1 biofilms was determined using synchrotron-based X-ray fluorescence microscopy (XRF). It was found that Fe, Mn, and Ca were mainly distributed near the air-biofilm interface of a biofilm grown on 40 mM citrate, while there were two Fe-, Mn-, and Ca-rich layers within a biofilm grown on 10 mM citrate. The sorption of copper by biofilm grown in medium containing 10 mM citrate was rapid, with copper being found throughout the biofilm after only 1 h of exposure. Copper initially colocalized with Fe and Mn element layers in the biofilm and then precipitated in a 40-µm-thick layer near the air-biofilm interface when exposed for 12 h. Cu K-edge X-ray absorption near edge structure (XANES) analysis revealed that Cu was primarily bound with citrate within the biofilm, and the precipitate formed in the biofilm exposed to copper for 12 h was most similar to copper phosphate. LIVE/DEAD staining revealed that cells at the biofilm-membrane interface were mostly alive even when the copper concentration reached 80.5 mg copper g(-1) biomass. This suggests that the biofilm matrix provided significant protection for cells in this area. These results significantly improve our understanding of metal acquisition, transportation, and immobilization in unsaturated biofilm systems.

Establishment of element fingerprint and multielement analysis of Fritillaria thunbergii by inductively coupled plasma optical emission spectrometry.

Element fingerprints were deciphered for Fritillaria thunbergii from Chinese ten major fritillaria-producing regions for the purpose of examining differences in element composition with region of origin and identifying elements' importance to F. thunbergii. Analysis by inductively coupled plasma optical emission spectrometry allowed simultaneous determination of 18 elements in F. thunbergii (Al, B, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Na, Mn, Mo, S, Ni, P, Pb, and Zn), and patterns in element concentrations were deciphered by principle component analysis (PCA) and hierarchical cluster analysis (HCA). The element fingerprint was established which well reflected the element characteristics of F. thunbergii. Meanwhile, the ten regions were discriminated with 100% accuracy using HCA and PCA based on 18 of these elements. The element Mg, Ca, K, B, P, Mo, Na, Cd, Ni, and Al were viewed as the characteristic element of F. thunbergii, and the fingerprint of these elements could be used to distinguish the authenticity of F. thunbergii Miq.