电子垃圾拆解对台州氯代/溴代二噁英浓度和组成的影响

电子垃圾拆解会导致有毒有害污染物向大气的排放,造成环境污染的产生。为了解电子垃圾拆解及废旧金属再生活动对拆解地及邻近地区空气质量的影响,对台州峰江金属再生园区附近及对照区路桥市区大气中(气态和颗粒态)氯代二噁英(PCDD/Fs)、溴代二噁英(PBDD/Fs)的含量、同系物组成及气/固分配规律进行了研究,通过相关性分析探讨了PCDD/Fs和PBDD/Fs的可能来源。结果显示,金属再生园区冬季采样期间17种2,3,7,8-PCDD/Fs和8种2,3,7,8-PBDD/Fs的平均浓度分别为212.2 pg·m-3和17.6 pg·m-3,夏季采样期间的平均浓度分别为84.5 pg·m-3和5.4 pg·m-3,均显著高于对照点。夏季采样期间对照点处于再生园区的下风向,其二噁英浓度高于冬季,说明其受到了金属再生园区的明显影响。基于相关性分析的结果,塑料焚烧是金属再生活动中氯代和溴代二噁英的主要来源。初步的暴露风险评价表明,金属再生园区附近居民每日摄入的二噁英含量远远超过世界卫生组织规定的人体每日耐受量(1~4 pg W-TEQ·kg-1·d-1)。上述研究结果为规范电子垃圾拆解活动提供了基础数据。     

溴代二噁英同位素稀释气相色谱/三重四极质谱法(GC/MS/MS)的建立与应用

建立了高灵敏度和高选择性的同位素稀释气相色谱/三重四极质谱法测定14种2,3,7,8位溴取代的二噁英同类物的痕量分析方法.结果表明,14种二噁英毒性同类物的平均相对响应因子的相对标准偏差均小于20%;校正曲线在0.1—500μg·L-1范围内显示良好线性(R20.99).仪器的检出限为0.08—4.00μg·L-1,满足PBDD/Fs的痕量分析需求.为验证方法的适用性,以再生铜冶炼飞灰样品为研究对象,利用所建立的方法测定了14种PBDD/Fs的含量,样品回收率范围在45%—120%之间,表明该方法可用于实际环境样品中PBDD/Fs的定性和定量分析.     

溴代二恶英类的来源、检测与污染现状

多溴二苯并-对-二恶英和多溴二苯并呋喃(PBDD/Fs)具有与多氯二苯并-对-二恶英和多氯二苯并呋喃(PCDD/Fs)相似的结构和毒性,广泛存在于多种环境介质和生物体中,已经引起了广泛的关注.本文讨论了溴代阻燃剂(BFRs)生产和处理、电子垃圾拆解和热处理、垃圾焚烧和金属冶炼等工业热过程中PBDD/Fs排放水平及生成机制.其中,PBDD/Fs在BFRs产品中的含量较高,范围为0.257—49.605μg.g-1,在电子垃圾热解处理中气相和固相的含量分别可达到57 ng TEQ.kg-1和19000 ng TEQ.kg-1,而在冶金过程烟道气中的含量范围是0.14—1.5 ng TEQ.m-3.本文还总结了PBDD/F分析方法研究进展,包括样品前处理和仪器分析方法,提出了目前影响准确定量PBDD/Fs的因素以及相关的解决措施.归纳了当前环境介质和生物体及食品中PBDD/Fs的存在水平,指出电子垃圾热处理、垃圾焚烧等工业热过程已导致周边环境和生物体内PBDD/Fs的浓度增高.最后,介绍了国外与PBDD/Fs相关的控制措施和政策法规.     

针铁矿催化氧化溴酚生成羟基多溴联苯醚和溴代二噁英

探究了针铁矿催化转化溴酚(2,4-DBP或2,4,6-TBP)生成羟基化多溴联苯醚(HO-PBDEs)和溴代二噁英(PBDD/Fs)的可能性.结果表明,针铁矿可以在常温和干反应条件下有效地催化转化溴酚化合物生成HO-PBDEs和PBDD/Fs.反应16 d,97.3%的2,4-DBP被针铁矿氧化转化,其中2.4%被转化为2'-OH-BDE-68,2.8%被转化为2,2'-OH-BB-80,0.2%被转化1,3,8-Tr BDD,0.4%被转化为2,4,6,8-Te BDF.同样的反应时间内,98.7%的2,4,6-TBP被针铁矿氧化转化,反应产物可能为2'-OH-BDE-121、4'-OH-BDE-121、1,3,6,8-Te BDD和1,3,7,9-Te BDD.根据检测到的产物,提出了针铁矿氧化转化溴酚的可能途径.     

四溴双酚A的光转化过程及机理

四溴双酚A(Tetrabromobisphenol A,简称TBBPA)作为目前使用最广泛的溴系阻燃剂,通过生产、使用、处置等环节进入到环境中,并通过环境降解过程转化为新型的有机污染物,产生未知环境风险.光转化是环境中有机污染物降解的主要方式之一,转化效率高、速度快.本文综述了TBBPA及其衍生物在光照条件下的模拟环境光转化和光催化过程及机理. TBBPA及其衍生物在光辐射条件下易发生转化,转化效率和速率受到pH、初始浓度、溶解氧等环境条件的影响,光催化剂会显著提升TBBPA的转化速率. TBBPA的光转化机理包括脱溴、β-断裂、羟基化等,产物主要包括三溴双酚A、二溴双酚A、4-异丙烯基-2,6-二溴苯酚、2,6-二溴苯酚、羟基化三溴双酚A等.相较于TBBPA,针对TBBPA衍生物的光降解过程和机理尚不明晰,未来需要进一步对TBBPA及衍生物光转化过程进行研究,为其迁移转化过程的机理和相关未知污染物的监控提供理论支持,为综合评估TBBPA类溴代阻燃剂的环境风险提供科学依据.     

Fe2+耦合热活化过硫酸盐降解土壤中四溴双酚A

有效降解和去除土壤中四溴双酚A(TBBPA)是土壤环境化学研究热点.本文研究了Fe²⁺耦合热活化过硫酸盐体系(Fe²⁺/热/PS)对土壤中TBBPA的降解,并考察温度、Fe²⁺始浓度、PS浓度、初始pH值、无机阴离子(Cl^-、HCO₃^-)浓度以及金属离子(Cu²⁺、Zn²⁺、Ni²⁺)浓度的影响.结果表明,Fe²⁺/热/PS降解TBBPA的效果远高于同等条件下单一热活化和Fe²⁺活化的情况;提高温度和PS浓度能够促进土壤TBBPA的降解;而过量的亚铁离子会导致TBBPA去除率下降,Fe²⁺与PS的最佳摩尔比为0.5:1;Fe²⁺耦合热活化PS体系具有较宽的pH应用范围,在酸性条件下更有利于降解;温度55℃、Fe²⁺浓度25 mmol·L^-1、PS浓度50 mmo...     

四溴双酚A在土壤中的降解转化及残留研究进展

四溴双酚A (tetrabromobisphenol A,TBBPA)是全球生产量最大的溴代阻燃剂,广泛应用于电子产品和塑料等高分子材料的生产中.由于高的亲脂性及环境稳定性,TBBPA在土壤中易于累积.土壤作为污染物主要的汇之一,污染物在土壤中的环境过程和归趋对正确评价污染物的环境风险至关重要.本文综述了土壤中TBBPA在不同氧化还原条件(无氧条件,连续无氧-有氧条件和有氧条件)下、植物(芦苇和水稻)或蚯蚓(Metaphire guillelmi和Eisenia fetida)存在时的降解、矿化、代谢路径、不可提取态残留(non-extractable residues,NERs)形成和稳定性,以及相关微观机理.TBBPA在无氧条件下脱溴降解为双酚A,并稳定地存在于无氧土壤中.有氧土壤中的TBBPA经过甲基化、本位取代,以及烷基链断裂生成多种代谢产物.植物和蚯蚓会改变土壤中TBBPA的归趋,具体表现为明显降低TBBPA矿化,增加甲基化(形成更多甲基醚类代谢产物),减少NERs形成.TBBPA及其代谢产物可以和土壤中有机质以酯键和醚键的方式形成NERs.土壤氧化还原状态的改变会使NERs释放TBBPA及其代谢产物,但水稻根系分泌物添加到土壤中对NERs的释放没有显著影响.未来需要进一步研究TBBPA在土壤中转化的微生物学机制、土壤中NERs的形成机制、在生物体内的转化体制、以及土壤中不同形态NERs和生物体内NERs的稳定性和生物效应等,为全面准确评估TBBPA的环境风险提供科学依据.     

改性海绵铁降解四溴双酚A的特性及机理

在超声条件下通过置换反应制备钯海绵铁(Pd0-s-Fe0)双金属颗粒,采用扫描电子显微镜(SEM)和电子能谱仪(EDS)进行表征.Pd0-s-Fe0催化还原降解溶液中的四溴双酚A(TBBPA)的实验结果表明,Pd0-s-Fe0较s-Fe0(海绵铁)催化活性高,在p H值为6.7,100 m L初始浓度为15 mg·L~(-1)溶液投加5 g负载0.07%钯的改性海绵铁的条件下,反应120 min后TBBPA的去除率达到91.5%,且Pd0-s-Fe0降解TBBPA符合一级动力学规律.经高效液相色谱串联四极杆飞行时间质谱(LC-TOF-MS)分析鉴定降解产物,明确TBBPA的还原降解途径为TBBPA被脱去1—4个溴生成三溴双酚A、二溴双酚A、一溴双酚A、双酚A.     

不同重金属对土壤中四溴双酚A环境归趋的影响

四溴双酚A(TBBPA)和重金属的复合污染情况常见于电子电器拆解厂或回收站周边土壤，而重金属对TBBPA在土壤环境中的降解、转化和残留的影响尚不清晰.本研究利用14C标记的TBBPA来探索不同浓度水平重金属(Cu、Cd和Zn)对两种土壤(红壤和乌栅土)中TBBPA降解转化、矿化、不可提取态残留形成等环境行为的影响.经60 d培养，乌栅土中92.2%±0.5%的TBBPA被转化为不可提取态残留或代谢产物，其中7.2%±0.8%被彻底矿化为CO2；灭菌作用极大地抑制了乌栅土中TBBPA不可提取态残留的形成(由77.2%降至9.9%)，表明土壤微生物在不可提取态残留的形成中起到关键作用.而红壤中仅有9.9%±0.5%的TBBPA被转化成不可提取态残留，<0.5%被矿化为CO₂，与灭菌对照组无显著差异.当土壤重金属(>500μmol·kg-1)存在时，乌栅土中TBBPA矿化和不可提取态残留形成率分别降低14%—78%和31%—86%，而可提取态TBBPA(即生物可利用态)增加0.5—4.4倍，其中水溶态残留增加0.3—1.5倍，进而增加TBBPA在土壤中的持久...     

四溴双酚A的水溶性与辛醇/水分配系数及其影响因素初探

用摇瓶法研究了pH值和金属离子对四溴双酚A(TBBPA)表观溶解度(SW*)的影响,并以摇瓶法考察了TBBPA在辛醇/水体系的分配行为,以及pH、pH与腐殖酸复合作用对分配行为的影响.结果表明,TBBPA表观溶解度受pH控制,在酸性条件下(pH<6.0)TBBPA水溶解度为0.15 mg·1-1,随着pH值增加,TBBPA逐渐解离,表观溶解度变大,pH在6.5-7.5范围内其Sw*-pH曲线呈指数增长趋势,pH7.5左右SW-pH曲线发生突变,pH 8.5后增长趋势平缓,pH 9.1时表观溶解度为26.5 mg·1-1.金属离子在pH值介于6.5-7.5之间会增大TBBPA的表观溶解度,pH 8.0后增溶作用减小.TBBPA的辛醇/水分配系数(1gKOW)为5.20,随pH值增大,TBBPA倾向于进入水相,pH值介于7.0-8.0时表观辛醇/水分配系数(lgDOW)随pH值增大以近线性趋势减小,且由此求得TBBPA的pKa1=7.2;腐殖酸能增大TBBPA的亲水性,且这种影响跟pH值和腐殖酸浓度有关,低浓度腐殖酸对TBBPA亲水性影响不大,随着腐殖酸浓度增大,TBBPA的亲水性显著增大了,但这种由腐殖酸浓度引起的TBBPA亲水性差异随pH值增大而缩小.     

磺胺甲恶唑对小麦叶片蛋白和叶绿素含量及SOD酶活性的影响

为了探明磺胺甲恶唑(sulfamethoxazole,SMZ)的生态毒理效应,通过实验室人工控制毒理实验,研究了低浓度SMZ暴露对小麦体内超氧化物歧化酶(SOD)活性、叶绿素(CHL)和蛋白质(SP)含量的影响.结果显示:染毒7d后,各浓度组小麦叶片的SOD活性均被显著诱导(P＜0.0l),并且染毒浓度的升高增强了SOD的活性,表明SMZ暴露胁迫下,小麦可启动自身的保护机制以最大限度地减少自由基损伤.而小麦叶片的CHL含量,随着SMZ染毒浓度的增加而逐渐降低.并且当SMZ暴露浓度较高时,小麦叶片的CHL含量被显著抑制(P＜0.05)).当SMZ染毒浓度为0.05～ 0.50 mg· L-1时,SP的含量被显著诱导(P＜ 0.01));1.00 mg·L-1SMZ对SP的含量产生显著(P＜0.01)抑制,这说明SMZ染毒剂量将对蛋白质的合成产生严重影响.综上,SOD的活性变化可反映出SMZ暴露对小麦的污染效应及其生态毒性作用,但将其作为评估SMZ污染暴露的生物标志物有待于进一步深入研究.     

磺胺甲恶唑暴露对小麦叶片蛋白和叶绿素含量及SOD酶活性的影响

为了探明磺胺甲恶唑(sulfamethoxazole,SMZ)的生态毒理效应,通过实验室人工控制毒理实验,研究了低浓度SMZ暴露对小麦体内超氧化物歧化酶(SOD)活性、叶绿素(CHL)和蛋白质(SP)含量的影响。结果显示:染毒7d后,各浓度组小麦叶片的SOD活性均被显著诱导(P<0.01),并且染毒浓度的升高增强了SOD的活性,表明SMZ暴露胁迫下,小麦可启动自身的保护机制以最大限度地减少自由基损伤。而小麦叶片的CHL含量,随着SMZ染毒浓度的增加而逐渐降低。并且当SMZ暴露浓度较高时,小麦叶片的CHL含量被显著抑制(P<0.05))。当SMZ染毒浓度为0.05～0.50mg·L-1时,SP的含量被显著诱导(P<0.01));1.00mg·L-1SMZ对SP的含量产生显著(P<0.01)抑制,这说明SMZ染毒剂量将对蛋白质的合成产生严重影响。综上,SOD的活性变化可反映出SMZ暴露对小麦的污染效应及其生态毒性作用,但将其作为评估SMZ污染暴露的生物标志物有待于进一步深入研究。     

毒死蜱(CPF)对克氏原螯虾的急性毒性及组织病理观察

采用静水生物测试法研究毒死蜱(CPF)对克氏原螯虾(Procambarus clarkii)的急性毒性效应及克氏原螯虾的组织病变情况并进行安全评价。设定0、2、10、20、40和80μg·L-1 6个CPF浓度梯度进行急性暴露试验,结果表明,CPF浓度升高对克氏原螯虾产生较大毒性,24、48和96 h半致死浓度〔ρ(LC50)〕分别为(28.24±2.81)、(19.50±2.03)和(13.13±1.70)μg·L-1,ρ(LC50)随着暴露时间延长呈显著下降趋势,符合双曲线衰减模型(r=0.999 9,P<0.000 1),安全浓度为(2.79±0.31)μg·L-1。组织病理观察发现,染毒虾心脏上皮细胞增生,心肌肌束间充满血淋巴细胞;神经细胞肿大,尼氏体溶解消失,细胞由多极形状变为圆形,神经纤维坏死并解体;肝胰腺小管收缩并充血,空泡增加;鳃组织空泡化,表面出现黑色素沉积,被多量血淋巴细胞浸润;肌肉纤维萎缩并溶解。     

外源Mo降低As(III)和As(V)对水稻的毒性及As的积累

通过溶液培养试验，研究外源添加Mo对2种价态砷(As(III)和As(V))胁迫下水稻吸收积累Mo和As的影响。结果表明，这2种价态的As对水稻生长均有抑制作用，As(III)比As(V)对水稻毒害更明显，添加Mo可缓解As对水稻的毒害。As添加可影响水稻根系和茎叶对Mo的吸收积累，但是不同价态As对Mo积累量的影响不一致。同时，Mo的添加也可以显著地降低水稻根系和茎叶对2个价态As的吸收积累。在100 μmol?L^-1 As(III)处理下，添加0.1和0.5 mg?L^-1的Mo可导致水稻根系As积累量分别比对照处理降低38.8%和52.8%，茎叶As积累量分别降低5.1%和10.6%；当As(V)浓度为100 μmol?L^-1时，添加0.1和0.5 mg?L^-1的Mo可导致水稻根系As积累量分别比对照处理降低15.4%和62.4%，茎叶As积累量分别降低11.9%和23.7%。Mo的添加还能显著地降低2种价态As在水稻根系和茎叶中的富集系数。因此，通过施用适量的Mo肥可以用来防治农田As污染，降低As对人体健康的危害。     

外源Mo降低As(Ⅲ)和As(Ⅴ)对水稻的毒性及As的积累

通过溶液培养试验,研究外源添加Mo对2种价态砷(As(Ⅲ)和As(Ⅴ))胁迫下水稻吸收积累Mo和As的影响。结果表明,这2种价态的As对水稻生长均有抑制作用,As(Ⅲ)比As(Ⅴ)对水稻毒害更明显,添加Mo可缓解As对水稻的毒害。As添加可影响水稻根系和茎叶对Mo的吸收积累,但是不同价态As对Mo积累量的影响不一致。同时,Mo的添加也可以显著地降低水稻根系和茎叶对2个价态As的吸收积累。在100μmol·L~(-1)As(Ⅲ)处理下,添加0.1和0.5 mg·L~(-1)的Mo可导致水稻根系As积累量分别比对照处理降低38.8%和52.8%,茎叶As积累量分别降低5.1%和10.6%;当As(V)浓度为100μmol·L~(-1)时,添加0.1和0.5 mg·L~(-1)的Mo可导致水稻根系As积累量分别比对照处理降低15.4%和62.4%,茎叶As积累量分别降低11.9%和23.7%。Mo的添加还能显著地降低2种价态As在水稻根系和茎叶中的富集系数。因此,通过施用适量的Mo肥可以用来防治农田As污染,降低As对人体健康的危害。     

Aerial defense of the nest by workers of the stingless bee Trigona (Tetragonisca) angustula (Latreille) (Hymenoptera: Apidae)

Summary The stingless bee Trigona (Tetragonisca) angustula has a sophisticated defense strategy against flying insect predators at the entrance of its nest. Groups of worker bees hover on both sides in front of the nest entrance tube, facing a flight corridor leading to the nest. Intruders which enter this corridor are attacked by these bees from the side and from behind and are forced to the ground by biting bees clinging to their wings. T. angustula is subject to predation by Lestrimelitta limao, a cleptobiotic stingless bee which performs organized raids on other nests to rob food supplies, larval provisions and nest constructing material. The presence of citral, released by L. limao during the raids, leads to a rapid increase in the number of hovering guard bees in front of T. angustula nests. This recruitment in response to citral suggests that the defense behavior in T. angustula has evolved under the pressure of L. limao raids and that citral functions in T. angustula as an alarm kairomone.     

Chemically mediated interactions between the red algaPlocamium hamatum (Rhodophyta) and the octocoralSinularia cruciata (Alcyonacea)

Interactions between the red algaPlocamium hamatum J. Agardh (Rhodophyta) and other benthic organisms including the alcyonacean soft coralSinularia cruciata (Tixier-Durivault) were investigated on an inshore fringing reef environment in whichP. hamatum was the dominant large fleshy alga. Field observations of sessile reef organisms including octocorals and sponges living in close proximity toP. hamatum revealed that varying degrees of tissue necrosis were suffered by the invertebrates when in physical contact with the alga. In order to establish whether the chemical constituents of the alga, especially chloromertensene, played a role in this necrosis, manipulative field experiments were carried out in the Pelorus Channel, Palm Island group (18°34S; 146°29E), North Queensland, Australia, in November and December 1988. The first experiment involved the relocation of healthy plants and soft corals into contact and non-contact situations on a mesh grid. In all cases of contact betweenP. hamatum andS. cruciata, the soft coral suffered tissue necrosis (n=6,p=0.0022). The second experiment had the same design, but involved the use of artificial plants both uncoated and coated with natural levels of chloromertensene, in contact withS. cruciata. In all cases of contact with coated treatments, necrosis was observed inS. cruciata (n=4,p=0.025). In cases where uncoated artificial fronds were placed in contact with soft corals,S. cruciata showed minor abrasion effects, but no appreciable necrosis. Coated treatments were not fouled by epiphytes during the experiment and were not consumed by predators. Uncoated treatments were rapidly reduced in size by predation and any remaining material was biofouled. These experiments thus demonstrated that the deleterious effects observed in soft corals in the field were caused by contact with the algaP. hamatum, that these effects were indeed chemically mediated by chloromertensene, and that physical contact without chemical intervention caused no such deleterious effects. This is the first experimental evidence which conclusively demonstrates allelopathy between an alga and other marine organisms and identifies the compound responsible for the observed allelopathic effects.     

胶州湾北岸潮间带三-(2,3-二溴丙基)异氰脲酸酯和六溴环十二烷的分布水平

对胶州湾北岸潮间带底泥样品中三-(2,3-二溴丙基)异氰脲酸酯(tris-(2,3-dibromopropyl)isocyanurate,TBC)和六溴环十二烷(hexabromocyclododecanes,HBCDs)的3种同分异构体(α-HBCD、β-HBCD、γ-HBCD)的分布水平进行分析,结合索氏提取与Waters ACQUITY UPLC-MS-MS超高效液相色谱-质谱联用仪检测出TBC和HBCDs的3种同分异构体α-HBCD、β-HBCD、γ-HBCD,浓度范围分别为1.20~5.62 ng·g~(-1)(干重)、1.18~1.54 ng·g~(-1)(干重)、1.50~1.85 ng·g~(-1)(干重)、2.12~2.99 ng·g~(-1)(干重)。其中,TBC在河流入海口处的浓度较高,γ-HBCD占ΣHBCDs的比例(44.75%)最高,且相关性分析表明TBC和HBCDs可能有相似的污染来源。最近,斯德哥尔摩公约持久性有机污染物审查委员会(POPRC)将HBCDs列入POPs名单加以限制使用,这表明其具有一定的环境风险,未来可能对环境和人类健康造成的危害应该引起足够的重视。     

Experimental tests of the information-center hypothesis with black vultures (Coragypsatratus) and turkey vultures (Cathartesaura)

In field tests of the information-center hypothesis (ICH) in south Texas with black vultures (Coragyps atratus) and turkey vultures (Cathartes aura), large carcasses were provided and kept under continuous observation. The use vultures made of these bait sites and their patterns of arrival were recorded to evaluate predictions derived from the ICH. Turkey vultures discovered most bait sites (30 of 31) first, but frequently were displaced from the food by later-arriving black vultures. This competitive exclusion by black vultures limited subsequent feeding opportunities for turkey vultures sufficiently that few (27%) returned on subsequent days to bait sites they had previously visited. I found no evidence that those turkey vultures that did return to bait sites acted as leaders for groups of naive birds and led them to bait sites – knowledgeable and naive turkey vultures did not arrive at bait sites together, and groups arriving at bait sites were not larger on subsequent days than on the first days carcasses were available. In contrast, a significantly larger percentage (47%) of knowledgeable black vultures returned to bait sites they had visited on previous days, and the first groups of black vultures arriving at bait sites on subsequent days were significantly larger than the equivalent groups on first days. Nine flocks of black vultures that arrived on subsequent days at bait sites before sunrise (which suggests the birds had commuted directly from a roost) contained knowledgeable birds, and two of these flocks contained both knowledgeable and naive individuals. Overall, 10 of 54 naive tagged black vultures (18.5%) arrived at bait sites under circumstances that suggested they had followed conspecifics to the food from a roost. However, most black vultures apparently found carcasses through independent search or by using local enhancement. Therefore, I conclude that while following from roosts to food sites is a strategy used by black vultures, at this study site it is one they use relatively infrequently. Received: 20 February 1997 / Accepted after revision: 28 June 1997