微塑料与农田土壤中典型污染物的复合污染研究进展

作为一种新型环境持久性污染物,微塑料除自身能够对生态系统产生不良影响外,其也可与周围环境中的共存污染物形成复合污染,从而产生更高的生态风险和健康风险.基于农业生态系统视角,聚焦重金属、农药和抗生素这3种农田土壤典型污染物与微塑料的复合污染,综述了重金属、农药和抗生素在微塑料上的吸附-解吸行为,探讨了微塑料的结构与性质、污染物的理化性质以及环境条件对重金属、农药和抗生素在微塑料上吸附-解吸行为的影响,阐述了微塑料对农田土壤中重金属、农药和抗生素生物有效性的影响及内在机制,指出了当前研究存在的问题和不足并对未来研究方向进行了展望,可为微塑料与农田土壤典型污染物复合污染的生态风险评估提供科学参考.     

Cu/Cr co-stabilization mechanisms in a simulated Al2O3-Fe2O3-Cr2O3-CuO waste system

• Cu and Cr can be mostly incorporated into CuFe_xAl_yCr_2−x−yO₄ with a spinel structure. • Spinel phase is the most crucial structure for Cu and Cr co-stabilization. • Compared to Al, Fe and Cr are easier to be incorporated into the spinel structure. • ‘Waste-to-resource’ by thermal process at attainable temperatures can be achieved. Chromium slag usually contains various heavy metals, making its safe treatment difficult. Glass-ceramic sintering has been applied to resolve this issue and emerged as an effective method for metal immobilization by incorporating heavy metals into stable crystal structures. Currently, there is limited knowledge about the reaction pathways adopted by multiple heavy metals and the co-stabilization functions of the crystal structure. To study the Cu/Cr co-stabilization mechanisms during thermal treatment, a simulated system was prepared using a mixture with a molar ratio of Al₂O₃:Fe₂O₃:Cr₂O₃:CuO= 1:1:1:3. The samples were sintered at temperatures 600–1300°C followed by intensive analysis of phase constitutions and microstructure development. A spinel phase (CuFe_xAl_yCr_2−x−yO₄) started to generate at 700°C and the incorporation of Cu/Cr into the spinel largely complete at 900°C, although the spinel peak intensity continued increasing slightly at temperatures above 900°C. Fe₂O₃/Cr₂O₃ was more easily incorporated into the spinel at lower temperatures, while more Al₂O₃ was gradually incorporated into the spinel at higher temperatures. Additionally, sintered sample microstructures became more condensed and smoother with increased sintering temperature. Cu / Cr leachability substantially decreased after Cu/Cr incorporation into the spinel phase at elevated temperatures. At 600°C, the leached ratios for Cu and Cr were 6.28% and 0.65%, respectively. When sintering temperature was increased to 1300°C, the leached ratios for all metal components in the system were below 0.2%. This study proposes a sustainable method for managing Cu/Cr co-exist slag at reasonable temperatures.     

广西典型岩溶区农田土壤-作物系统Cd迁移富集影响因素

为揭示岩溶区农田土壤-作物系统Cd迁移富集主要影响因素,选择广西典型岩溶区根系土-水稻籽实Cd含量及土壤pH值、有机质（OM）、氧化物含量和质地数据,通过Spearman相关性分析和主成分分析（PCA）,开展了土壤理化性质对土壤和水稻籽实Cd含量的影响研究.结果表明,相比于全国土壤背景基准值,研究区土壤中总氧化铁（TFe₂O₃）、三氧化二铝（Al₂O₃）和氧化锰（MnO）相对富集,平均含量分别为20.2%、19.0%和0.2%,且区内广泛发育Fe-Mn结核;而二氧化硅（SiO₂）相对亏损,平均含量为41.0%,呈现出典型的"脱硅富铝铁"特征,表明研究区土壤经历了较强烈的风化淋溶作用.相关性分析结果显示,土壤TFe₂O₃和MnO含量分别与土壤总Cd含量和残渣态Cd百分比呈显著的正相关性,与有效态Cd含量、水稻籽实Cd含量和Cd的生物富集系数（BCF）呈显著的负相关性.PCA分析结果也显示,土壤TFe₂O₃和MnO含量是影响土壤-作物系统Cd迁移富集的主要因素,而土壤pH值、OM和Al₂O₃含量等影响程度较小,SiO₂含量和土壤质地间接地影响土壤-作物系统Cd的迁移富集.综合研究认为,土壤在交替氧化和还原条件下所形成的新生体Fe-Mn结核对Cd具有较强的吸附和固定作用,导致Cd在残渣态中相对富集,降低了土壤Cd的活动性,因此Fe-Mn结核是研究区土壤Cd生物有效性的主要影响因素.     

Effect of lime on speciation of heavy metals during composting of water hyacinth

Composting is attractive and inexpensive method for treatment and biomass disposal of water hyacinth. However, the major disadvantage of water hyacinth composting is the high content of heavy metals in the final compost. Addition of lime sludge significantly reduced most bioavailable fractions (exchangeable and carbonate) of heavy metals. Studies were carried on composting of water hyacinth (Eichhornia crassipes) with cattle manure and sawdust (6:3:1 ratio) and effects of addition of lime (1%, 2% and 3%) on heavy metal speciation were evaluated during 30 days of composting period. The Tessier sequential extraction method was employed to investigate the changes in speciation of heavy metals such as Zinc (Zn), Copper (Cu), Manganese (Mn), Iron (Fe), Lead (Pb), Nickel (Ni), Cadmium (Cd) and Chromium (Cr) during water hyacinth composting. Effects of physicochemical parameters such as temperature, pH and organic matter on speciation of heavy metals were also studied during the process. Results showed that, the total metal content was increased during the composting process. The higher reduction in bioavailability factor (BF) of Cu, Fe, Ni, Cd and Cr was observed in lime 2 treatment about 62.1%, 64.4%, 71.9%, 62.1% and 58.9% respectively; however higher reduction in BF of Zn and Pb was observed in lime 1 treatment during the composting process. Reducible and oxidizable fractions of Ni, Pb and Cd were not observed during the process. Addition of lime was very effective for reduction of bioavailability of heavy metals during composting of water hyacinth with cattle manure and sawdust.     

厦门汀溪水库溶解有机氮对有毒藻种的生物有效性及其化学本质

为探究厦门汀溪水库溶解有机氮(DON)对有毒藻种的生物有效性及其化学本质,采用水样分子质量和极性分级技术,进行铜绿微囊藻 (Microcystis aeruginosa)培养实验.结果表明,汀溪水库中DON含量呈季节性差异,在枯水期比较高,而丰水期比较低.汀溪水库DON在不同季节中的主要成分都是疏水组分和>3kDa组分.汀溪水库DON的生物有效性为65.20%.较疏水组分和>3kDa组分而言,亲水组分和￡3kDa组分DON更易被铜绿微囊藻利用.从水环境和水源保护角度出发,应首先考虑消除DON中的亲水性组分和小分子质量组分.     

Detection and quantitation of trace levels of low molecular weight halocarbons (LMHs) associated with commercial sodium humate

Examination of vapor above commercial sodium humate and above 10wt% aqueous humate solution by gas chromatography (GC) revealed the presence of chloroform and trichloroethylene. Further examination of the aqueous humate by the purge and trap procedure confirmed the association of chloroform and trichloroethylene with the humate. GC/mass spectrometry analyses of methylene chloride extract of the humate established the association of LMHs with the humate. Improved headspace capillary GC technique showed that the humate contained not only chloroform, trichloroethylene but several other LMHs in the range 190 to 4000ng·kg^‐1.     

Effect Of pH on the complexation of U(II) with organic matter dissolved in resh waters

In the present work we study the effect of pH on the complexation of copper with organic matter dissolved in fresh surface waters. Samples collected in rivers of Galicia (NW of Spain) were titrated with copper solution at pH values in the range 5.5–7.5. Copper concentration was measured by DPASV technique. The complexation parameters were obtained from the simple model of 1 : 1 complex formation. The obtained values show a linear increase of the logarithm of the conditional stability constant as the pH increases.     

Bioavailability of copper and cadmium in sediment of nanjing section of Changjiang river to aquatic organisms

Bioavailabilities of metals in sediment to aquatic organisms depend on the strength of metal bonding to particulates. The accumulation tests of Cu and Cd in carp and in snails have been studied in vitro with the solution containing semisynthetic sediment samples in which the contents of various speciation of metal in sediment have been extended. For carp, the accumulation of Cu and Cd is related to the concentration of dissolved metal which in turn is affected by the distributions of speciations in sediment under given environmental conditions. It is another pattern for snails, various speciations of metal in sediment can contribute indirectly to metal accumulation. The contribution ratio, or relative importance of various speciations of metal in sediment can be expressed by multiple linear regression formulas. The contribution of ion‐exchangable speciation and coprecipition with carbonate speciation is 10⁵ times larger than that of residue speciation in sediment.     

Potentiometric studies of mixed complexes of cobalt(II) and copper(II) with l‐Asparagine and adenine

A potentiometric titration technique has been used to determine the stability constants for the various complexes of Co(II) and Cu(II) with L‐asparagine and from DNA base, e.g. adenine. Stability constants of ternary systems have been evaluated by the method suggested by Irwing‐Rossotti. In addition, the conditional constants were calculated as a function of pH. The maximum values of the conditional formation constants were found to be in accordance with the mixed‐ligand complex formation constants in a determined pH region. Furthermore, the molar fractions of different species from mixed complexes were calculated by means of formation constants. The values of stability constants of mixed‐ligand complexes at 25°C are as follows: log K= 5.25 for Co(II)‐L‐asparagine‐adenine; log K= 9.30 for Cu(II)‐L‐asparagine‐adenine. The ionic strength was kept constant at I = 0.20 with NaClO₄.     

Relationships Between Copper Species and Forms,Hydrographic and Biomass Parameters in the Taiwan Erhjin Chi Coastal Area

The first incident of green oysters (Crassostrea gigas) was reported in Taiwan in the Charting coastal area in January, 1986 and mortality was reported three months later. the cause of the greened oysters was identified as copper pollution. the copper content of the green oysters was extremely high - 2100 ppm, 2225 ppm, and 4400 ppm dry weight, in January, 1986, February 1987, and January 1989, respectively. in this paper we summarize the seasonal and regional distributions of copper species (complexed by inorganic and organic ligands, labile and non-labile, polar and non-polar) and forms (dissolved and particulate) and the hydrographic and biomass parameters (mainly particulate organic carbon, chloropyll -α, adenosine triphosphate and primary production) in sea water in the Erhjin Chi coastal area. in general, high concentrations of particulate material (0.24 to 724 ppb) and non-labile organic copper (0.03 to 21.5 ppb) were observed. Low values of polar organic copper (<0.02 to 16.5 ppb) indicated that non-polar organic complexes (0.3 to 20.4 ppb) from man-made organic pollutants were the major complexes in the area studied. On the basis of this data, the cause of greening and mortality in oysters is evaluated in relation to the bioavailable copper (sum of particulate and labile copper) and copper assimilative capacity (detoxicant). Finally, the correlations between the species and forms of copper, hydrographic and biomass parameters are also discussed.