Recycling of non-metallic fractions from waste electrical and electronic equipment (WEEE): A review

The world’s waste electrical and electronic equipment (WEEE) consumption has increased incredibly in recent decades, which have drawn much attention from the public. However, the major economic driving force for recycling of WEEE is the value of the metallic fractions (MFs). The non-metallic fractions (NMFs), which take up a large proportion of E-wastes, were treated by incineration or landfill in the past. NMFs from WEEE contain heavy metals, brominated flame retardant (BFRs) and other toxic and hazardous substances. Combustion as well as landfill may cause serious environmental problems. Therefore, research on resource reutilization and safe disposal of the NMFs from WEEE has a great significance from the viewpoint of environmental protection. Among the enormous variety of NMFs from WEEE, some of them are quite easy to recycle while others are difficult, such as plastics, glass and NMFs from waste printed circuit boards (WPCBs). In this paper, we mainly focus on the intractable NMFs from WEEE. Methods and technologies of recycling the two types of NMFs from WEEE, plastics, glass are reviewed in this paper. For WEEE plastics, the pyrolysis technology has the lowest energy consumption and the pyrolysis oil could be obtained, but the containing of BFRs makes the pyrolysis recycling process problematic. Supercritical fluids (SCF) and gasification technology have a potentially smaller environmental impact than pyrolysis process, but the energy consumption is higher. With regard to WEEE glass, lead removing is requisite before the reutilization of the cathode ray tube (CRT) funnel glass, and the recycling of liquid crystal display (LCD) glass is economically viable for the containing of precious metals (indium and tin). However, the environmental assessment of the recycling process is essential and important before the industrialized production stage. For example, noise and dust should be evaluated during the glass cutting process. This study could contribute significantly to understanding the recycling methods of NMFs from WEEE and serve as guidance for the future technology research and development.     

上海大气超细颗粒物和工业纳米颗粒的表征及细胞毒性的比较研究

采集了上海市石洞口地区2010年春季不同粒径大气颗粒物样品,使用ICP-AES和FESEM技术分析了颗粒物的化学组成和微观特征,比较了不同粒径的大气颗粒物与3种工业纳米颗粒物的生物活性.结果表明,在染毒剂量为25、50、100和200μg.mL-1时,大气颗粒物水溶组分和不溶组分及工业纳米颗粒均可以抑制A549细胞生长活性并能诱导细胞产生活性氧(ROS),且大气细颗粒水溶组分生物活性最强,在上述染毒剂量下对细胞生长活性的抑制率分别达到13.31%、18.15%、20.43%和23.78%.在纳米尺度的颗粒物染毒组分中,纳米NiO的生物活性最强,在上述染毒剂量下对细胞生长活性的抑制率分别达到11.81%、15.12%、17.62%和19.44%.因此,大气细颗粒物水溶组分是最主要的毒性成分.     

Environmental significance of biogenic elements in surface sediments of the Changjiang Estuary and its adjacent areas

Biogenic elements and six phosphorus(P) fractions in surface sediments from the Changjiang Estuary and adjacent waters were determined to investigate the governing factors of these elements, and further to discuss their potential uses as paleo-environment proxies and risks of P release from sediment. Total organic carbon(TOC) and leachable organic P(Lea-OP) showed high concentrations in the estuary, Zhejiang coast and ofshore upwelling area. They came from both the Changjiang River and marine biological input.Biogenic silicon(BSi) exhibited a high concentration band between 123 and 124°E. BSi mainly came from diatom production and its concentration in the inshore area was diluted by river sediment. Total nitrogen(TN) was primarily of marine biogenic origin. Seaward decreasing trends of Fe-bound P and Al-bound P revealed their terrestrial origins. Influenced by old Huanghe sediment delivered by the Jiangsu coastal current, the maximum concentration of detrital P(Det-P) was observed in the area north of the estuary. Similar high concentrations of carbonate fluorapatite(CFA-P) and CaCO3 in the southern study area suggested marine calcium-organism sources of CFA-P. TOC, TN and non-apatite P were enriched in fine sediment, and Det-P partially exhibited coarse-grain enrichment, but BSi had no correlation with sediment grain size. Diferent sources and governing factors made biogenic elements and P species have distinct potential uses in indicating environmental conditions. Transferable P accounted for 14%-46% of total P. In an aerobic environment,there was low risk of P release from sediment, attributed to excess Fe oxides in sediments.     

抚仙湖不同来源沉积物磷形态垂向分布特征

采用连续萃取法(SEDEX)对抚仙湖岸带代表不同污染来源的5个样点和湖心沉积物中磷形态的分布特征及垂向变化特征进行分析.结果表明,沉积物中无机磷(IP)是总磷(TP)的主要组成部分,占TP的70.46％ ±8.06％;磷形态以碎屑磷灰石(CAP)和闭蓄态磷(Org-P)为主,分别占TP的41.65％±17.04％和29.53％±8.06％,而可交换态磷(Ex-P)含量最低,仅占TP的2.42％±1.45％.不同点位TP含量和各形态磷分布特征不同,以磷矿开采污染为主的东大河口沉积物总磷含量及各形态磷含量远高于其它污染来源的沉积物,其中CAP含量达(131.46±84.78)μmol·g-1.沉积物磷形态垂向特征表征了流域人类活动对抚仙湖的污染历程.东大河口沉积物各形态磷含量随深度变化剧烈,尤其是CAP在8～14 cm随深度增加突然增大后又急剧降低,且均在11 cm处达最大值,这与抚仙湖流域磷矿开采兴起到矿点关闭的历史相吻合.湖心沉积物磷形态分布特征显示了湖岸各种污染来源“汇”的特点.     

微生物对冰封期湖泊沉积物中有机磷降解释放的影响

以寒旱区湖泊乌梁素海为研究对象,以有机磷降解过程中的形态转化为主线,探讨了冰封期内底物添加与灭菌处理对有机磷释放特征的影响.结果表明,180 d冰封期内,灭菌处理(T_N)上覆水中可溶性总磷酸盐(DTP)和可溶性正磷酸盐(DIP)及可溶性有机磷(DOP)的质量浓度均高于底物添加处理(T_M),揭示T_M体系中厌氧微生物的同化利用降低了上覆水中磷的质量浓度;同时微生物驱动下铁的异化还原作用也是影响水-沉积物界面有机磷释放的重要机制.释放周期内,沉积物中活性有机磷(LOP)、总活性磷(TLP)的含量均减少;T_M体系的中等活性有机磷(MLOP)含量先减少后增加,非活性有机磷(NLOP)的含量先增加后减少;T_N的MLOP含量波动性增加,NLOP的含量波动性减少.释放初期(0~60 d),T_M的MLOP含量高于T_N,而NLOP的含量低于T_N;释放中末期(60~180 d),T_M的MLOP含量低于T_N,而NLOP的含量高于T_N.揭示释放中沉积物MLOP与NLOP之间存在相互转化的可能性.释放过程中,T_M沉积物有机磷的相对含量降低,无机磷的相对含量增高,呈现有机磷向无机磷转化的趋势,沉积物有机磷约有6.1%转化为无机磷,揭示了冰封期内,微生物可加速沉积物有机磷向无机磷的转化,提高了磷的生物可利用率,增加了沉积物磷向上覆水释放的风险.     

太湖流域农村黑臭河流沉积物中磷形态的垂向分布特征

为揭示太湖地区农村黑臭河流表层沉积物中磷形态的分布特征及各形态磷之间的相关性,本文以宜兴市周铁镇掌下浜(北段)为例,沿河流从上游到下游河口共采集了13个表层沉积物样,应用SMT法(The Standards,Measurements and Testing Programme)对柱状沉积物中磷形态进行了分析,并对有机质与各磷形态及其之间进行相关性分析.结果表明:在垂向分布上,沉积物中各形态磷含量随深度加深总体均呈现下降趋势;总磷(Total Phosphorus,TP)的平均含量为659.33~4379.31 mg·kg-1,无机磷(Inorganic Phosphorus,IP)构成沉积物中磷的主要部分,占TP的66.59%~88.25%;盐酸提取态磷(Hydrochloric acid extractable phosphorus,Ca-P)占TP的44.17%~71.47%,占IP的62.17%~83.70%,是构成IP的主要部分.有机质含量与各形态磷之间皆表现出显著的正相关性,反映出垂向沉积剖面上有机质是磷形态含量的重要影响因素.IP、Ca-P、OP(Organic Phosphorus,有机磷)与TP均具有显著的相关关系,表明沉积物中TP含量的增加,主要来自Ca-P,其次是OP;沉积物中OP与Fe/Al-P(NaOH extractable phosphorus,铁铝磷)、Ca-P含量也具有显著的正相关关系,表明OP含量对Fe/Al-P、Ca-P的含量均有影响;Ca-P与Fe/Al-P含量之间存在显著的相关性,说明沉积物中Fe/Al-P的还原释放对Ca-P的形成具有一定的影响.     

不同Zn水平下辣椒体内Cd的积累、化学形态及生理特性

采用盆栽试验研究了重金属Cd(20mg·kg-1)污染下,叶面喷施不同浓度Zn(0、100、200、400、600μmol·L-1)对辣椒生长、叶绿素含量、抗氧化酶活性以及辣椒体内Cd形态和积累量的影响.结果表明,在Zn≤400μmol·L-1范围内,辣椒叶、茎、根、果实干重及叶片叶绿素a、b含量随Zn浓度不断增加而增加;高量Zn(600μmol·L-1)抑制了辣椒的生长、降低了叶片叶绿素含量.在Zn≤400μmol·L-1范围内,辣椒叶SOD和CAT活性随Zn浓度增加而降低,辣椒叶的超氧化物歧化酶(SOD)和过氧化氢酶(CAT)活性在400μmol·L-1Zn时达到最低,当Zn400μmol·L-1时,SOD和CAT活性呈上升趋势.叶面喷施Zn使辣椒茎、根及果实中Cd含量分别降低了2.7%～5.4%、7.5%～28.1%和7.6%～21.8%.与对照相比较,叶面喷施Zn的辣椒果实Cd总提取量、氯化钠提取态Cd、去离子水提取态Cd以及乙醇提取态Cd含量分别降低了7.7%～21.8%、4.11%～23.6%、54.5%～66.8%和4.8%～86.7%,但醋酸提取态和残渣态增加了28.0%～68.0%和12.6%～25.0%.     

电动脱除孔隙水削减底泥内源磷的效果研究

选择污染严重的底泥为研究对象,采用基于孔隙水脱除的电动修复装置,进行了底泥脱水排磷实验,探究了电动脱除孔隙水的底泥减磷效果,分析了底泥各形态磷在电动脱除孔隙水中的迁移转化过程.结果表明：电动脱水过程中阴极总脱水量为5740mL,远大于阳极（2121mL）,但脱水中总磷浓度为阳极大于阴极,80%以上的磷从阳极排出,电迁移在电动脱水排磷中起主要作用,通电使排磷总量增加了70%以上,其中在0.25V/cm的电压梯度下修复18d的条件下,排磷量最大;电动脱水排磷效率在通电48h内达到最高[0.73mg/（kW·h）],随后急剧减小;经过电动脱水排磷后,底泥含水率下降了14.07%,底泥总磷降幅最高可达231.92mg/kg,底泥中交换态磷（Ex-P）、铁结合态磷（Fe-P）、闭蓄态磷（Oc-P）、钙结合态磷（Ca-P）平均脱除率分别为80.01%、14.75%、40.65%和19.22%,其中阳极酸化导致氧化铁的溶解和Ca-P的释放,故阳极附近Oc-P、Ca-P降幅较大,而阴极碱化使Fe-P释放,故阴极附近Fe-P降幅较大.经计算可知,通过电动脱除孔隙水,底泥中生物可利用性磷（Ex-P+Fe/Al-P）平均下降了14.12%,底泥内源磷释放的风险得以降低.     

三峡水库蓄水至175 m后干流沉积物理化性质与磷形态分布特征

为研究三峡水库蓄水至175 m后干流沉积物总磷(TP)及各形态磷的分布状况,2010年10月采集了乌江、茅坪等13个断面表层沉积物样品,分析了有机质、矿物成分、粒径等理化参数,测定了沉积物总磷、可交换态磷(Ex-P)、铝结合态磷(Al-P)、铁结合态磷(Fe-P)、闭蓄态磷(Oc-P)和钙结合态磷(Ca-P)的含量,探讨了磷形态赋存与沉积物理化性质间的相关性,评估了蓄水对沉积物磷的蓄积及生物可利用性的影响.结果表明,三峡水库干流沉积物有机质含量为7.79~55.63g·kg~(-1),主要矿物成分为绿泥石、伊利石和石英.沉积物的主要组成为黏土质粉砂,中值粒径(d_(50))范围为3.84~23.65μm.沉积物总磷含量为557.06~837.92 mg·kg~(-1),各采样点总磷富集指数均大于1,存在潜在的磷污染风险.沉积物磷形态以CaP和Oc-P为主,Ex-P、Fe-P和Al-P含量相对较低,生物可利用性磷仅占总磷含量的2%~8%.与历史资料相比,蓄水后三峡水库沉积物的粒径有细化变小的趋势,易风化矿物组分含量略有增加,蓄水水位的增加并未导致沉积物总磷含量出现明显升高趋势.未来,随着三峡水库来沙进一步减少和泥沙颗粒的逐渐细化,磷在三峡水库部分宽谷河段沉积物有可能逐步蓄积;蓄水运行过程引起的大面积消落带干湿交替以及近坝段浮泥再悬浮都将影响沉积物中磷的生物可利用性水平.     

碱浸钢丝污泥热处理后的重金属形态及浸出特性

为了分析碱浸钢丝污泥热处理后的重金属形态及浸出特性,以ALRS（碱浸钢丝污泥）为研究对象,通过批处理试验,研究了热处理温度对ALRS中Pb和Zn浸出特性及其化学形态的影响,并运用重金属综合毒性指数模型（STI）对热处理ALRS中Pb、Zn的综合毒性进行了评估.结果表明:高温热处理使得ALRS的物相成分发生改变,钙-铁复合氧化物分解,形成单一铁氧化物及钙氧化物.热处理使得ALRS中Pb、Zn总量有一定程度增加,而其浸出量随处理温度升高而降低,Pb、Zn最大释放量与总量的最大比值仅为0.52%.BCR连续提取法结果表明,ALRS中Pb、Zn形态主要是以残渣态和可氧化态形式存在,酸溶态含量较低,分别为2.84%和8.94%.经热处理后,Pb和Zn的残渣态含量（F4）明显增加,酸溶态（F1）、可还原态（F2）、可氧化态（F3）3种形态含量减少,两种重金属的稳定态含量与不稳定态含量比值[（F3+F4）/（F1+F2）]分别在900和800℃时取得最大值（22.86和10.61）.综合毒性评估结果表明,STI值由原状样品的0.065减至900℃下样品的0.046,重金属综合毒性和生态风险显著降低.研究显示,热处理可增加碱浸剩余污泥中Pb、Zn的稳定性,降低其生态风险.