典型地区农用地污染调查及风险管控标准探讨

针对《土壤污染风险管控标准——农用地土壤污染风险管控标准》(GB 15618—2018),提出以土壤中全量浓度筛选值和管控值作为衡量农用地土壤污染风险管控的标准,对湖南省部分稻田农用地土壤及点对点稻米样品中镉、铅、砷、汞的总量和有效态浓度及稻米中含量进行监测,根据重金属总量浓度分为低风险、中风险、高风险3组。结果显示:(1)土壤及稻米中镉含量基本为随着风险级别的升高而增加,铅、砷在土壤和稻米中含量无规律性结果,汞监测结果均为未检出。(2)低风险组稻米镉超标率为12. 0%,高风险组稻米镉达标率为33. 3%,表明利用总量浓度对农用地土壤潜在风险进行分组存在一定的局限性。(3)依据4种重金属在土壤中总量及稻米(早稻)中含量情况,对风险级别进行调整并综合判断:有58个样品为低风险组,占样品总数的68. 2%,超标率为零;有15个样品为中风险组,占样品总数的17. 7%,超标率为80. 0%;有12个样品为高风险组,占样品总数的14. 1%,超标率为100. 0%。调整后评价结果与上述标准的划分目标更接近,能够提高上述标准的准确性和实用性。     

Catalytic degradation of toxic organic dye using an aluminum-doped Cu0.4Zn0.6-xAlxFe2O4 (x = 0.0, 0.2, 0.4, 0.6) spinel ferrite in a photo-Fenton system

Catalytic activity of spinel ferrite in breaking down toxic dye materials are promising due to their uniqueness. In this study, aluminum-doped copper zinc ferrite, Cu_0.4Zn_0.6-xAl_xFe₂O₄ (x = 0.0, 0.2, 0.4, 0.6), a catalyst for toxic dye degradation is synthesized through chemical co-precipitation route. The formation of the spinel ferrite catalyst is initially confirmed by Fourier transform infrared spectra, which shows the frequency of metal-oxygen bond vibration at 539 and 427 cm⁻¹ attributed to the tetrahedral and octahedral sites respectively. Higher intensity sharp peak of X-ray diffraction for (311) plane is the evidence for the phase purity and the formation of spinel ferrite. The crystallite size is found to decrease with the increase of Al³⁺ ion. The surface structure of the obtained particles is investigated using a scanning electron microscope. Analyses of the material's magnetic characteristics using a vibrating sample magnetometer (VSM) revealed that it is, in fact, a soft magnet, as evidenced by the loop of its hysteresis, which is narrow. The catalytic degradation of methylene blue dye under the mechanism of the photo-Fenton process is studied with the obtained spinel ferrites and the result is found to be as high as 96.5%. The process follows pseudo-second order kinetics and the Langmuir isotherm.     

大肠杆菌吸附-化学还原法用废含金催化剂制备金纳米线

采用大肠杆菌吸附-化学还原法,以大肠杆菌(ECCs)为模板、十六烷基三甲基溴化铵为保护剂、抗坏血酸为还原剂,由废含金催化剂制备金纳米线(AuNWs)。采用XRD,SEM,TEM等技术对AuNWs进行表征。研究了AuNWs对罗丹明6G(R6G)和4-巯基苯甲酸(4-MBA)的拉曼散射信号的增强效果。实验结果表明:在制备过程中加入微生物ECCs,可使金回收率提高约20百分点;当溶液pH小于4时,反应2 h后,有大量呈线状的AuNWs聚集沉降,金回收率可达99%1以上。表征结果显示,AuNWs呈多晶结构,晶格间距为0.23 nm。表面增强拉曼散射分析表明,AuNWs对R6G和4-MBA具有良好的拉曼光谱增强性能。     

Feasibility of honeycomb monolith supported sugar catalyst to produce biodiesel from palm fatty acid distillate (PFAD)

Carbon coated monolith was prepared by sucrose solution 65 wt.% via dip-coating method. Sulfonation of incomplete carbonized carbon coated monolith was carried out in order to synthesize solid acid catalyst. The textural structure characteristics of the solid acid catalyst demonstrated a low surface area and pore volume. Palm fatty acid distillate (PFAD), a by-product of palm oil refineries, was utilized as oil source in biodiesel production. The esterification reaction subjected to different reaction conditions was performed by using the sulfonated carbon coated monolith as heterogeneous catalyst. The sulfonation process had been performed by using vapour of concentrated H₂SO₄ that was much easier and efficient than liquid phase sulfonation. Total acidity value of carbon coated monolith was measured for unsulfonated sample (0.5 mmol/g) and sulfonated sample (4.2 mmol/g). The effect of methanol/oil ratio, catalyst amount and reaction time were examined. The maximum methyl ester content was 89% at the optimum condition, i.e. methanol/oil molar ratio (15:1), catalyst amount (2.5 wt.% with respect to PFAD), reaction time (240 min) and temperature 80 °C. The sugar catalyst supported on the honeycomb monolith showed comparable reactivity compared with the sugar catalyst powder. However, the catalyst reusability studies showed decrease in FFA% conversion from 95.3% to 68.8% after four cycles as well as the total acidity of catalyst dropped from the value 4.2 to 3.1 mmol/g during these cycles. This might be likely due to the leaching out of SO₃H group from the sulfonated carbon coated monolith surface. The leaching of active species reached a plateau state after fourth cycle.     

Economies of scale in global iron-making

In this paper, we investigate the presence of economies of scale in the global iron-making industry for integrated steel plants, iron making being the first stage in the steel-making process. Iron making depends on basic commodities, such as iron ore, coke and various forms of energy, required in the operation of the blast furnace, which can be classified as essential inputs and used in fixed proportions to produce iron. A generalized Leontief cost function is estimated using panel data for 69 integrated plants, such a specification being appropriate for technologies with essential inputs that are used in fixed proportions in production. A significant scale effect is observed due to the existence of fixed costs and a linear dependence of the cost function on production. Under a simple linear cost function, a rough estimate of the breakeven scale of plant, where costs equal revenue, is 4.5 Mt per year. Competitiveness, as measured by the ratio of plant average cost per tonne to best practice cost per tonne, can be shown to be positively related to the scale of production as well as the cost of essential inputs. Therefore, low-cost producers are also often producers with low raw material costs and production levels below the estimated breakeven scale of operation. Labor costs, although significant, are comparatively less important as a driver towards low costs.     

基于GIS的南京市典型蔬菜基地土壤重金属污染现状与评价

对南京市八卦洲蔬菜基地土壤中的铅、铬、铜和镉进行测定分析,利用不同的评价标准来评价其环境质量状况,同时借助GIS软件研究了污染指数的空间分布状况,并解析了其重金属污染的来源.结果表明,以自然背景值为评价标准,则蔬菜地土壤中的重金属都超过污染指标,其中镉为首要污染因子;以国标二级为评价标准,则除镉以外的三种重金属的单项污染指数值全都小于1,但其综合污染指数迭1.50,总体上属轻污染状况.南京化工因区、南京长江二桥和各种农业生产活动等可能是主要污染源.     

Isolation and Identification of Enterococci from Seawater Samples: Assessment of Their Resistance to Antibiotics and Heavy Metals

A hundred Enterococcus strains were isolated from seawater samples collected from coastal areas of Istanbul. Isolates were identified to the species level using standard biochemical tests specified by Facklam and Collins. The species distribution was as follows Enterococcus faecalis (96%), Enterococcus gallinarum (3%) and Enterococcus solitarius (1%). The resistance of bacteria to both heavy metals (zinc [Zn], iron [Fe], cadmium [Cd], chrome [Cr], cobalt [Co]) and antibiotics (ampicillin 10 μg [AP], penicillin G 10 Units [PG], gentamycin 10 μg [GM], streptomycin 10 μg [S], chloramphenicol 10 μg [C], erythromycin 15 μg [E], kanamycin 30 μg [K], amikacin 30 μg [AK], nalidixic acid 30 μg [NA], and vancomycin 30 μg [VA]) was evaluated. None of the strains was resistant to VA. It was found that among the 100 isolates, those that exhibit resistance to antibiotics, particularly NA, S and K, were also resistant all the heavy metals tested. To our knowledge this is the first report focusing on determination of resistance of environmental enterococci found in Istanbul against heavy metals and antibiotics. Thus, combined expressions of antibiotic and heavy metal resistance may help to reinforce ecological and epidemiological studies and to determine the role of these strains in antibiotic and heavy metal resistance dissemination.     

Metals in vineyard soils of the Penedès area (NE Spain) after compost application

The application of organic wastes to improve soil physical characteristics in mechanized vineyards planted after land levelling is becoming a common practice in Mediterranean areas. It may be useful as an additional source of organic matter and nutrients, but these wastes could also have negative effects due to their metal content. The aim of the study was to evaluate the influence of compost application on soil metal contents in mechanized vineyard soils of the Spanish Mediterranean area, where this practice is repeated every three years. The study was carried out in a ten-year-old vineyard where the main soil type is Typic Calcixerept. Composted cattle manure was applied in alternate rows, at a rate of 40 Mgha(-1) dry-weight. Nine sampling points were located along the slopes of two plots: a levelled plot prepared for mechanization with large soil disturbance movements within the plot, and a plot of undisturbed soil. At each location, soil samples were taken in both treated and untreated soils. Total concentrations (digestion with aqua regia) and the extractable DTPA (Diethylene-triaminepentacetic)-CaCl2-TEA (Triethanolamine) fractions of Cu, Zn and Mn were analyzed in each sample. For Cu and Zn, the initial concentration was higher in the undisturbed plot. In both cases, total Cu and total Zn were positively affected by manure input and the concentration in treated soils was significantly higher than in untreated soil. For Mn, the initial concentration was higher in disturbed soils than in undisturbed ones, and although in both scenarios the concentrations increased with manure, no significant differences were found between treated and untreated soils. The extractable fraction also increased in treated versus untreated soils, although for Cu and Mn the extractable/total metal ratio was similar in treated and untreated soils. After one compost application, total metal contents increased significantly, particularly for Zn. Most of those metals are accumulated in the soil, due to the soil characteristics.     

Removal of aqueous lead by poorly-crystalline hydroxyapatites

The use of a phosphorus amendment in altering Pb to a chemically less mobile phase is a promising strategy based on minimizing ecotoxicological risk and improving time and cost efficiency. This study evaluated crystalline and poorly-crystalline hydroxyapatite sorbents on removal of aqueous Pb in response to reaction time, solution pH, and Pb concentration. Batch experiments were conducted using a commercially-available crystalline hydroxyapatite (HA), and two poorly-crystalline hydroxyapatites synthesized from gypsum waste (CHA) and incinerated ash of poultry waste (MHA). Poorly-crystalline hydroxyapatites had greater capacity for Pb removal from a solution with a wider pH range as compared to a crystalline hydroxyapatite. The maximum sorption capacity of Pb determined by the Langmuir model was 500 mg g⁻¹ for CHA, 277 mg g⁻¹ for MHA and 145 mg g⁻¹ for HA. Removal of aqueous Pb by CHA was not dependent on solution pH, with a 98.8% reduction throughout the solution pH range of 2–9, whereas aqueous Pb removal by HA and MHA was pH-dependent with less removal in the neutral solution pH. Poorly-crystalline hydroxyapatites may provide an effective alternative to existing remediation technologies for Pb-contaminated sites.     

铅锌矿区玉米中重金属污染特征及健康风险评价

以西南某铅锌矿区为研究区域,测定了92份玉米样品中Pb、Zn、Cd、Cr和Ni的含量,开展了矿区玉米籽粒中重金属污染特征及健康风险研究.应用单因子污染指数和内梅罗综合污染指数分析了重金属在玉米中的污染状况,采用健康风险评价模型评价了重金属对人体健康造成的风险,同时利用主成分分析法解析了重金属的主要来源.结果表明,玉米籽粒中Pb、Zn、Cd、Cr和Ni的平均含量分别为0.30、23.75、0.21、1.33和1.15 mg ·kg^-1;除重金属Zn外,其他4种重金属均超过我国食品卫生标准限值,研究区玉米籽粒中Pb、Cd、Cr和Ni的综合污染指数范围介于4.32~9.07之间,均属于重度污染,Zn的综合污染指数小于1;重金属通过玉米籽粒摄入引起的复合重金属污染对成人和儿童均存在健康风险,且对儿童造成的健康风险高于成人.玉米籽粒中5种重金属可以由2个主成分来反映,第一主成分主要支配Pb、Cd、Cr和Ni的来源,第二主成分支配Zn的来源.玉米籽粒重金属含量与土壤重金属含量之间没有明显相关性.