羟基乙叉二膦酸镀铜废液的处理及Cu~(2+)的高附加值资源化回收

采用Na BH4还原法将羟基乙叉二膦酸(HEDP)镀铜废液中的Cu~(2+)制备成纳米铜粉,并采用聚丙烯酰胺(PAM)对还原反应后的废液进行絮凝处理。研究了n(Cu~(2+))∶n(Na BH4)、还原反应温度、还原反应时间及PAM添加量对废液中剩余Cu~(2+)质量浓度的影响,并对回收的纳米铜粉进行了XRD和TEM表征。实验结果表明:当n(Cu~(2+))∶n(Na BH4)=4∶6、还原反应温度为50℃、还原反应时间为2 h时,废液中剩余Cu~(2+)质量浓度降低至1.1 mg/L,Cu~(2+)还原率达99.99%;可获得粒径为20~45 nm的近球型、高纯度、由多晶组成的纳米铜粉;当PAM添加量为10 mg/L时,废液中剩余Cu~(2+)质量浓度降至0.35 mg/L以下,达到GB 21900—2008《电镀污染物排放标准》(小于0.5 mg/L)的要求。     

Co-treatment of fruit and vegetable waste in sludge digesters. An analysis of the relationship among bio-methane generation,process stability and digestate phytotoxicity

The co-digestion of a variable amount of fruit and vegetable waste in a waste mixed sludge digester was investigated using a pilot scale apparatus. The organic loading rate (OLR) was increased from 1.46 kg VS/m³ day to 2.8 kg VS/m³ day. The hydraulic retention time was reduced from 14 days to about 10 days. Specific bio-methane production increased from about 90 NL/kg VS to the maximum value of about 430 NL/kg VS when OLR was increased from 1.46 kg VS/m³ day to 2.1 kg VS/m³ day. A higher OLR caused an excessive reduction in the hydraulic retention time, enhancing microorganism wash out. Process stability evaluated by the total volatile fatty acids concentration (mg/l) to the alkalinity buffer capacity (eq. mg/l CaCO₃) ratio (i.e. FOS/TAC) criterion was <0.1 indicating high stability for OLR <2.46 kg VS/m³ day. For higher OLR, FOS/TAC increased rapidly. Residual phytotoxicty of the digestate evaluated by the germination index (GI) (%) was quite constant for OLR < 2.46 kg VS/m³ day, which is lower than the 60% limit, indicating an acceptable toxicity level for crops. For OLR > 2.46 kg VS/m³ day, GI decreased rapidly. This corresponding trend between FOS/TAC and GI was further investigated by the definition of the GI ratio (GIR) parameter. Comparison between GIR and FOS/TAC suggests that GI could be a suitable criterion for evaluating process stability.     

Comparative analysis of anaerobically digested wastes flow properties

The flow curve of anaerobically digested wastes from different origins was determined through rheological measurements. Regardless of their origin, samples can be divided into two families: simple non-Newtonian liquids well modelled by basic power law below 10%DC and viscoelastic liquids with a yield stress, well modelled by a Herschel–Bulkley model above. In all the cases, the rheological behaviour is driven by both the organic content and the volatile fraction (organic content/solid content), indicating that anaerobic digestion tends to smooth the rheological characteristics of organic wastes, whichever their origins.     

Total and Methylmercury in Soft Tissues of White-Tailed Eagle (Haliaeetus albicilla) and Osprey (Pandion haliaetus) Collected in Poland

Mercury (Hg) contamination in piscivorous birds, especially methylmercury (MeHg), has been drawing much attention worldwide in regard to its bioaccumulation and biomagnification in food chains. In this study on Hg in the soft tissues of white-tailed eagles (n = 22) and ospreys (n = 2) from Poland, total Hg (THg) range was 0.15–47.6 while MeHg range was 0.11–8.05 mg kg⁻¹ dry weight. In both species, median THg and MeHg concentrations were lower in the muscle and brain than in the liver and kidney. Median nephric residues were just under 3 and 5 mgTHg kg⁻¹ or 0.9 and 3.7 mgMeHg kg⁻¹ for white-tailed eagle and osprey, respectively. In Norwegian data from the 1970s and in our results, MeHg in the muscle of white-tailed eagle was ~60 % THg (%MeHg = MeHg/THg × 100), lower than in other piscivorous birds. A clear similarity in THg tissue levels was found between Polish and German populations of white-tailed eagles.     

Production costs and operative margins in electric energy generation from biogas. Full-scale case studies in Italy

The purpose of this study was to observe the economic sustainability of three different biogas full scale plants, fed with different organic matrices: energy crops (EC), manure, agro-industrial (Plants B and C) and organic fraction of municipal solid waste (OFMSW) (Plant A). The plants were observed for one year and total annual biomass feeding, biomass composition and biomass cost (€ Mg^?1), initial investment cost and plant electric power production were registered. The unit costs of biogas and electric energy (€ Sm^?3_biogas, € kW h^?1_EE) were differently distributed, depending on the type of feed and plant. Plant A showed high management/maintenance cost for OFMSW treatment (0.155 € Sm^?3_biogas, 45% of total cost), Plant B suffered high cost for EC supply (0.130 € Sm^?3_biogas, 49% of total cost) and Plant C showed higher impact on the total costs because of the depreciation charge (0.146 € Sm^?3_biogas, 41% of total costs). The breakeven point for the tariff of electric energy, calculated for the different cases, resulted in the range 120–170 € MW h^?1_EE, depending on fed materials and plant scale. EC had great impact on biomass supply costs and should be reduced, in favor of organic waste and residues; plant scale still heavily influences the production costs. The EU States should drive incentives in dependence of these factors, to further develop this still promising sector.     

便携式GC-MS法快速测定固定污染源废气中的VOCs

采用便携式GC-MS法快速测定固定污染源废气中VOCs,32种VOCs在2×10~(-7)~1×10~(-6)范围内线性良好,方法检出限为2×10~(-9)~1×10~(-8),标准气体样品6次测定结果的RSD为1.9%~19.1%,环境空气样品的加标回收率为66.2%~116%。在实际现场监测固定污染源中VOCs时,使用速查(Survey)功能可初步判断样品浓度,确定稀释倍数。比对试验结果表明,气袋和玻璃注射器采样法对VOCs测定结果无显著性差异。     

采用支持向量机算法优化电化学处理油田污水的工艺参数

采用支持向量机(SVM)算法,将Box-Behnken设计法与支持向量回归算法(SVR)实验参数优化软件相结合,优化电化学去除油田污水COD的工艺参数。通过量子粒子群算法对SVM算法参数进行优化,从建立的回归模型中找到工艺参数的全局最佳点:电解时间60 min,电解电流3 A,三维电极填充料中石英砂质量695 g。模型得到的COD理论最优去除率为92.48%,验证实验得到的COD去除率为91.43%。     

沈阳市固定燃烧源挥发性有机化合物2007年排放清单研究

挥发性有机化合物(VOCs)与.OH的反应是对流层臭氧形成的重要化学过程,是导致城市光化学烟雾的根本原因。为建立沈阳市固定燃烧源VOCs排放清单,选取了电力热力行业、钢铁行业和秸秆燃烧3个主要排放源进行研究。结果表明:(1)2007年,沈阳市固定燃烧源VOCs排放总量为8 544.539 t,其中排放量最大的是秸秆燃烧,为6 317.115 t;其次是电力热力行业,为2 225.780 t;最小的是钢铁行业,为1.644 t。(2)沈阳市各区县固定燃烧源VOCs排放量由大到小排序依次为新民市、法库县、东陵区、康平县、辽中县、于洪区、苏家屯区、大东区、沈北新区、铁西区、沈河区、皇姑区、和平区;VOCs排放强度由大到小排序依次为大东区、沈河区、铁西区、东陵区、皇姑区、和平区、于洪区、苏家屯区、法库县、康平县、辽中县、沈北新区、新民市。     

Variability of dust iron solubility in atmospheric waters: Investigation of the role of oxalate organic complexation

Atmospheric dust deposition is a major external iron source for remote surface ocean waters. Organic complexation is known to play a role in the dissolution of iron-containing minerals. In this paper, we present our study on the effect of oxalate on dust iron solubility in simulated rainwater. Our results reveal that the solubility of iron carried by analogs of different African dusts varies with the dust source. Our experiments indicate a positive linear correlation between iron solubility and oxalate concentration. Soluble iron (SFe) increases from 0.0025(±0.0005)% to 0.26(±0.01)% of total iron, considering all dust sources and with oxalate concentrations ranging from 0 to 8 μM. These results show that the observed variability of iron solubility in aerosols collected over the Atlantic Ocean is, at least partly, due to an increase in dust iron solubility, with the presence of oxalate complexation, rather than to the presence of more soluble anthropogenic iron. Considering the mineralogical composition of those particles, experiments with pure minerals (hematite, goethite and illite) were performed to study the dissolution process. We found that oxalate promotes the solubility of iron contained in clay and hence confirmed that more than 95% of SFe from soil dust is provided by clay (illite). This experimental work enables us to establish a parameterization of iron solubility in dust as a function of oxalate concentration and based on the individual iron solubility of pure iron-bearing minerals usually present in dust particles. Finally, our results emphasize that oxalate contributes to iron solubility on the same order of magnitude as the acid processes. Organic complexation appears to be a process that increases iron solubility and likely enhances the bioavailability of iron from dust.     

水体中常见无机阳离子对TiO2薄膜光催化还原Cr（Ⅵ）的影响

选择了6种水体中常见的阳离子（Na^＋、Mg^2＋、Ca^2＋、Al^3＋、Cu^2＋、Ni^2＋）,分别考查了其对TiO2薄膜光催化还原Cr（Ⅵ）的影响;从光吸收、无机离子本身的性质对光生电子的捕获及传递等讨论了上述离子影响TiO2薄膜光催化还原Cr（Ⅵ）的反应速率的原因。结果表明：由于其不能捕获光生电子,Na^＋、Mg^2＋、Ca^2＋本身对TiO2薄膜光催化还原Cr（Ⅵ）的反应速率影响不大;Al^3＋吸引电子能力较强,成为光生电子和Cr（Ⅵ）之间的桥梁,促进了Cr（Ⅵ）的还原;浓度为1 mmmol/L时,Cu^2＋显著地促进了Cr（Ⅵ）的光催化还原,其主要原因是Cu^2＋捕获光生电子的能力很强,起到了催化剂的作用,而浓度大于10 mmol/L时,Cu^2＋形成单质Cu以及对紫外光的吸收都使促进作用降低;Ni^2＋未充满的d轨道具有获得并传递光生电子的能力,也促进了Cr（Ⅵ）的还原;在浓度同为1mmol/L时,对Cr（Ⅵ）光催化还原的促进作用依次为：Cu^2＋〉Al^3＋〉Ni^2＋〉Na^＋、Ca^2＋、Mg^2＋。