离子型稀土采矿对矿山及周边水土环境的影响

离子型稀土矿开采造成的水土环境问题具有潜在性、持续性的特点。文章选择中国南方典型离子型稀土矿山,对研究区内135 km2的地表水、地下水以及矿山内的表层土壤、深层土壤进行系统的采样、分析,以查明稀土采矿对矿山及周边地区水土环境的影响范围和程度。结果表明:离子型稀土矿开采对矿区及周边地区水土环境产生了不同程度的影响。矿区地表水酸化,p H值降低,分布范围为3.6~5.8,水中稀土总量为363~117 520μg/L、Pb含量为361~1 550μg/L、SO42-含量为214~1 121μg/L、NH4+含量为33.7~268μg/L、NO3-含量为90~468μg/L,这些指标超过国家《地表水环境质量标准》(GB3838-2002)或当地地表水的背景值。空间分布表现为,矿区内地表水化学环境受到的影响最为严重,矿区外围的地表水次之,矿区及周边及矿区周围地下水基本未受影响。矿区土壤受采矿活动的影响,表现为矿区深层土壤严重酸化,表层土壤p H值分布范围为4.5~6,深层土壤为3~4。矿区深层土壤(地下150 cm之下)大量富集SO42-、NH4+-N、NO3--N、NO2--N,含量分布范围为34~90、5~73、34~304、33~115 mg/kg分别是背景值的2~3、20~24、18~20、3~6倍,存在潜在的生态风险。     

典型废旧塑料处置地土壤中多溴联苯醚污染特征

选择我国北方典型废旧塑料处置地为研究区域,对土壤中21种PBDEs(多溴联苯醚)的含量、同系物组成和分布特征进行了研究. 结果表明,该区域土壤中w(∑PBDEs)为1.25~3673.41ng/g,平均值为749.29ng/g,其中w(BDE209)占w(∑PBDEs)的92%以上. 整体上,处置作坊内土壤中w(∑PBDEs)明显高于作坊间道路土壤和处置地周边土壤. 塑料中添加的十溴联苯醚工业品是该区域土壤中PBDEs的主要来源. 该区域土壤PBDEs污染水平与我国电子废物集中处置场地相当,高出我国一般城市及工业城市土壤1~3个数量级,是我国另一类PBDEs高污染区,其环境风险性应引起足够的重视.      

电子废物拆解区农业土壤中多溴二苯醚的分布与来源

用GC-NCI-MS测定了浙江台州路桥表层农业土壤中41种多溴二苯醚(PBDEs)的含量, 并对其分布及来源进行了分析.结果表明:所有样品中Σ41PBDEs的含量为0.193~91.0ng/g,平均值为8.96ng/g,其中BDE209的含量为0.0452 ~ 61.5ng/g,平均值为5.41ng/g.在多数样品中十溴BDE及九溴BDEs是主要的同族体,四溴和七溴BDEs同族体次之.同族体组成特征和聚类分析表明,多数采样点主要受到deca-BDE工业品的污染,另有一些采样点受到octa-BDE和deca-BDE工业品的污染,个别采样点主要受到penta-BDE工业品污染.与国内外相关研究相比,研究区域内土壤中PBDEs的污染水平较低,但少数采样点受点源污染影响较大.     

苏州、无锡和南通道路灰尘中的多溴联苯醚和多氯联苯

2009年7月在江苏省南部城市苏州、无锡和南通采集了58个城市道路灰尘样品,使用气相色谱质谱法测定了样品中的8种多溴联苯醚(PBDEs)和32种多氯联苯(PCBs).结果表明,样品中Σ8PBDEs含量范围为4.21~1 471μg·kg-1,Σ32PCBs含量范围为ND~14.1μg·kg-1,PBDEs的含量远远高于PCBs.和其他地区城市土壤样品比较,城市道路灰尘中的PBDEs含量较高,来自燃料燃烧过程和汽车尾气产生的PBDEs不容忽视.城市工业区和中心区样品中PBDEs和PCBs的含量水平没有显著性差异,而高于景观区.研究发现,在城市工业区存在PCBs非故意排放源.PBDEs同族体单体相对含量分析表明,BDE209是样品中检测出的最主要的PBDEs单体,占Σ8PBDEs含量的96.7%(64.1%~99.8%).样品中的PCBs同族体主要为四氯代PCBs和六氯代PCBs,道路灰尘中PCBs同族体的分布模式与PCBs产品和其他环境介质存在一定差异.     

广州市室内尘土中多溴联苯醚的分布特点及来源

随机采集了广州市46个家庭和12个办公室内尘土样品,同时采集了17个室外尘土样品、2个电视机和2个电脑尘土样品并分析了室内尘土中多溴联苯醚(PBDEs)的含量、单体分布及来源.结果表明,家庭尘土中∑10PBDEs(BDE28,47,66,85,99,100,153,154,183,209之和)的含量为 564.3~9654ng/g,中值和均值分别为 2686,3407ng/g;办公室尘土中∑10PBDEs 的含量为 1737~4408ng/g,中值和均值分别为3133,3179ng/g.室内尘土中PBDEs的最主要单体为BDE209,分别占家庭尘土和办公室尘土∑10PBDEs的97.4%和99.0%.BDE47、99和183在室内尘土中含量也较高.大多数室内尘土中∑10PBDEs的含量高于室外,说明室内可能有重要的PBDEs释放源.室内尘土中PBDEs的主要工业品来源为十溴联苯醚,五溴联苯醚次之,八溴联苯醚较少.     

典型电子废物焚烧区水生生物多溴联苯醚累积特征

对广东清远某电子废物焚烧区封闭水体中水生生物体PBDEs(多溴联苯醚)的累积特征进行了研究. 结果表明,草虾、田螺、河蚌、鲫鱼、鲤鱼、黄鳝和乌鳢等水生生物体内w(∑₂₁PBDEs)(以脂肪质量计)为0.2487~24.50μg/g. 该电子废物焚烧区水生生物PBDEs污染较严重,较我国其他地区开放性水体的水生生物体w(PBDEs)高出1~3个数量级. 其中,底栖动物河蚌和田螺体内PBDEs累积最高,w(∑₂₁PBDEs)分别为11.38和4.968μg/g. 不同同系物在水生生物体内累积差异较大,BDE209是水生生物体PBDEs累积的主要组分,占49.83%~91.48%,八溴代和九溴代BDE也发生了高累积. 营养级是电子废物焚烧区水生生物PBDEs累积的最主要控制因素,但捕食和生活习性对生物体尤其是软体动物PBDEs累积也产生了较大影响.      

家庭尘土中多溴联苯醚的含量及人体暴露水平初步研究

在广州和海口随机采集了52个家庭尘土样品,用GC/MS定量分析了样品中∑10PBDEs(BDE28,47,66,85,99,100,153,154,183,209之和)的含量、单体组成模式和可能的影响因素,并估算了成年人和婴幼儿通过尘土摄入对PBDEs的暴露水平.结果表明,所有样品中都检出PBDEs,∑10PBDEs的含量范围为544.2～9 654 ng/g,中位值和平均值分别为2 547 ng/g和3 096 ng/g,广州样品中∑10PBDEs含量明显高于海口样品.尘土中PBDEs含量与家用电器和含聚氨酯泡沫家具数量、电器使用时间没有显著相关性.家庭尘土中PBDEs的主要成分是BDE209,其平均含量高达3 021 ng/g,占∑10PBDEs含量的73.70%～99.74%,平均值为96.85%.BDE47、99和183是∑9PBDEs(BDE209除外)中含量最丰富的单体,其含量均值分别为24.48%、23.99%和21.66%,广州和海口样品的单体组成没有显著区别.成年人和婴幼儿通过尘土摄入对PBDEs的暴露水平分别为10.59～254.7 ng/d和140.1～509.3 ng/d,由于婴幼儿的尘土摄入量远大于成年人,其对PBDEs的暴露水平也明显偏高.尘土摄入是人体暴露于PBDEs的重要途径,对婴幼儿更是如此.     

北方某典型活动区地下水中PBDEs/PFASs的污染特征

地下水水源中持久性有机污染物的污染将直接威胁人体健康,已成为地下水安全的重点问题之一。选择典型农业活动区天津市某区重要蔬菜种植基地,研究该区地下水中多溴联苯醚(PBDEs)和全氟类化合物(PFASs)的污染分布及其特征,并评价潜在风险。结果表明,该区地下水中PBDEs浓度水平为0~33.71 ng/L(平均浓度为5.43 ng/L),而土壤中PBDEs平均浓度(10.34 ng/g d.w.)高于地下水,存在PBDEs随降雨等条件由土壤渗入地下水的风险。地下水中75%检出BDE-209(十溴联苯醚),推测该区受高溴代阻燃剂产品污染为主。该区地下水中总PFASs浓度为0.321~8.284 ng/L(平均浓度2.413 ng/L),且10类PFASs均有检出,其中以短碳链的全氟辛烷磺酸(PFOS)(0~2.38 ng/L)和长碳链全氟辛酸(PFOA)(0.025~3.94 ng/L)为主。     

某电子废弃物拆卸区土壤、水和农作物中砷含量状况研究

为研究电子废弃物拆卸、废旧金属冶炼等是否对周围环境造成砷积累和污染,选取浙江省台州路桥区为调查对象,通过测定在该区采集的水、沉积物、土壤以及稻米和蔬菜中的砷,以了解该地区环境中砷的含量特征和潜在风险,并对土壤-水稻系统砷的分布和吸收转运规律进行了初步分析.结果表明,地表水和地下水砷含量平均值分别为 8.26μg/L和18.52μg/L,部分地下水超过WHO推荐的饮用水标准(10μg/L),但没有超过我国相关环境标准Ⅲ级限值(50μg/L).沉积物砷含量平均值为9.62mg/kg.水田土壤和菜地砷含量平均值分别为7.11mg/kg和6.17mg/kg,均在一级标准范围内,该区农田土壤总体上未受砷的污染.糙米和蔬菜中的砷平均值分别为165.1μg/kg和144.2μg/kg,均未超过我国规定的食品卫生标准.土壤-米糠-糙米中砷含量之间相关性显著.冶炼源周围的土壤和米糠中砷含量较其他源高,可能已经对周围土壤-水稻砷积累产生影响.     

沈阳地区地表水、浅层地下水及沿岸土壤中苯系物的污染分布

对沈阳地区主要地表水(浑河、细河、蒲河、沈抚灌渠)及其沿岸地下水和土壤中苯系物(BTEX)的污染特点和分布特征进行了研究.结果表明:细河和沈抚灌渠地表水中BTEX检出率较高(33%~67%),苯和甲苯是该区域的主要污染物,ρ(苯)和ρ(甲苯)分别为0.30~24.90和0.30~354.00μg/L;地表水检出的BTEX均未超过《生活饮用水卫生标准》(GB5749—2006)的限值(1 510μg/L).细河两岸的浅层地下水在一定程度上受到BTEX的污染,苯和甲苯的检出率分别为25%~33%和13%~25%,二甲苯和乙苯检出率较低(0~20%).彰驿镇19个监测井中有2个浅层地下水监测井中的ρ(苯)超过GB5749—2006限值(10μg/L),夏季ρ(苯)最大值为236.00μg/L.沿岸附近土壤中5种BTEX全部被检出,检出率均高于相应的河水.研究区包气带土壤层虽具有良好的防污性能,但也具有储存和阻碍BTEX挥发和降解的负面效应,对当地的生态系统和人类健康构成了潜在的威胁.     

基于氢氧稳定同位素的华北农田夏玉米耗水规律研究

农作物耗水规律的研究对提高农业用水效率,缓解我国华北地区的水资源短缺现状具有重要意义。论文基于水文监测与氢氧稳定同位素方法,以山西省运城市董村农场为例,研究了夏玉米在不同生长期的根系吸水深度变化,以及农田灌溉条件下SPAC系统的水分通量。研究结果表明,夏玉米拔节期、开花期和成熟期的主要根系吸水深度分别为0~20 cm(96%~99%)、20~50 cm(58%~85%)、0~20 cm(69%~76%),在整个生长期内存在着先由浅变深,后由深变浅的规律;夏玉米漫灌后,蒸腾量占蒸散发量的71.3%,深层入渗损失量占到灌溉水量的43.3%,灌溉水的利用率仅为40.4%,应采取措施减小深层入渗量以提高灌溉水利用率。     

某市再生水灌区水土环境中PPCPs污染特征分析

为初步了解再生水灌区土壤环境中药物与个人护理品（PPCPs）的污染特征,识别灌区地下水中PPCPs的主要来源,对某市东南郊Y灌区内的淸灌区、再生水灌区以及湿地三种类型的场地进行了精细剖面钻探工作,采集不同深度土壤、灌区地表水及成井地下水样品,分别对其进行了常规指标和15种PPCPs浓度的测试.结果表明,不同场地土壤中PPCPs含量分布存在差异,土壤剖面中PPCPs含量总体表现为再生水灌区 > 清灌区 > 湿地.土壤中PPCPs总浓度平均值为15.6μg/kg,主要以卡马西平CBZ、苯扎贝特BF、吉非罗齐GF、氯霉素CP、吲哚美辛IM为主.灌区地表水中PPCPs总含量明显高于地下水,总浓度平均值分别为272.5ng/L和63.5ng/L,且地表水中,PPCPs含量呈现沿程递减现象.利用Multi-cell基本原理并结合推流的概念刻画PPCPs从地表穿透土壤包气带进入地下水的垂向输移过程,计算结果显示除卡马西平CBZ、甲芬那酸MA和萘啶酸NA外,其余9种PPCPs计算值和地下水中的实测值吻合良好,初步证实再生水是灌区地下水中PPCPs的主要来源.     

Effects of nitrogen and phosphorus concentrations on the bioaccumulation of polybrominated diphenyl ethers by Prorocentrum donghaiense

The growth, cellular total lipids, bioaccumulation amount, and bioaccumulation factors (BAFs) of 2,4,4 ′ -tribromodiphenyl ether (BDE28), 2,2 ′ ,4,4 ′ -tetrabromodiphenyl ether (BDE47), and 2,2 ′ ,4,4 ′ ,5-pentabromodiphenyl ether (BDE99) in a semi-continuous culture of Prorocentrum donghaiense were studied in relation to nitrate (0, 128, and 512 μmol/L) and phosphate (0, 8, and 32 μmol/L) concentrations. The BDE28, BDE47, and BDE99 content per cell under 0 μmol N/L were 3.77 × 10 6 , 3.95 × 10 6 , and 4.32 × 10 6 ng/cell, respectively, which were significantly higher than those under 128 and 512 μmol N/L. A nearly 5-fold increase in polybrominated diphenyl ether (PBDE) content per algal cell was found between 0 and 8 μmol P/L and between 8 and 32 μmol P/L. With increasing N and P concentrations, the PBDE content per volume of algal culture and the accumulation percentage of available PBDEs declined slightly. The BAFs for the PBDEs based on lipids showed that the logBAF lip under 0 μmol N/L was higher than those under 128 and 512 μmol N/L. The logBAF lip under 0 μmol P/L was higher than that under 8 μmol P/L but lower than that under 32 μmol P/L. Correlation analysis indicated a significant negative correlation between nutrient concentration and cellular total lipids, as well as the PBDE content per cell. The results indicate that different N and P concentrations change the total lipids content of P. donghaiense, thereby resulting in varying PBDE accumulation.     

多溴联苯醚在电子废弃物拆卸地沉积物中的垂直分布

采用气相色谱质谱联用仪对采自清远电子废弃物拆卸地水库钻孔沉积物中的多溴联苯(polybrominated diphenyl ethers,PBDEs)进行了分析,调查其在沉积物中的垂直分布.结果表明,PBDEs在所有的样品中均检出,含量为0.43～141 ng/g,平均为9.26 ng/g.PBDEs在下层(16 cm以下)沉积物中含量较低、变化很小(0.43～2.30 ng/g),但在上层沉积物中含量明显增加(2.90～141 ng/g),反映了当地电子废弃物拆卸活动的影响;3种工业源的PBDEs,即五溴、八溴和十溴PBDEs,表现出相似的垂向分布趋势,说明其来源的一致性.其中,十溴PBDEs是最主要的PBDEs,平均占所有PBDEs的79.6%,其次是五溴PBDEs(14.7%),而八溴PBDEs所占比例最低(5.69%).3种PBDEs的组成模式显示,它们与相应的工业品PBDEs组成都有一定差异,可能因其降解行为不同所致.一些PBDE的同族体组成在沉积钻孔的垂直变化也进一步说明高溴代PBDE在沉积物的埋藏期间可能发生了降解,虽然还需要进一步研究证实.     

温度和停留时间对十溴联苯醚在污染土壤中热脱附的影响

采用自配十溴联苯醚污染土壤开展热脱附试验研究,试验温度分别为200、300、325、350、400和450 ℃,停留时间为10、20、30、40、50和90 min. 分析多溴联苯醚(PBDEs,包括BDE28、BDE47、BDE66、BDE99、BDE100、BDE138、BDE153、BDE154、BDE183、BDE190、BDE196、BDE197、BDE203、BDE205、BDE206、BDE207、BDE208和BDE209)热脱附前后污染物在土壤中的浓度及总脱附率. 试验用土样中w(PBDEs)为1 136.69 mg/kg. 低温段(200和300 ℃)污染物去除率较低,在300 ℃、停留时间90 min时,残留w(PBDEs)为263.57 mg/kg,去除率为76.81%;中温段(325和350 ℃)污染物大量减少,350 ℃、停留时间40 min时,残留w(PBDEs)为114.01 mg/kg,去除率达90%;高温段(400和450 ℃),温度为450 ℃、停留时间20 min时,残留w(PBDEs)为4.81 mg/kg,去除率达99%以上. 结果表明,PBDEs去除率随温度或停留时间的增加而增大,处置试验用土样比较合理的热脱附操作条件:温度为400 ℃、停留时间为20 min.      

Ecotoxicological effects of mixed pollutants resulted from e-wastes recycling and bioaccumulation of polybrominated diphenyl ethers in Chinese loach （Misgurnus anguiUicaudatus）

To understand potential ecotoxicological e ects of electrical and electronic equipment waste (e-waste) recycling and polybrominated diphenyl ethers (PBDEs) bioaccumulation in loaches, a semi-field experiment using Chinese loach (Misgurnus anguillicaudatus) as experimental fish was performed. Larval loaches were kept in net-cage for three months in an e-wastes recycling site and a reference site in Southeastern China. There was significant di erence of the survival rate between the loaches from the e-wastes recycling site (27%, 19/70) and from reference site (70%, 49/70). Histopathological responses were also found in all the livers examined in loaches from the e-wastes recycling site. These results showed that mixed pollutants resulted from e-wastes recycling led to ecotoxicological e ects on loaches. The bioaccumulation of polybrominated diphenyl ethers (PBDEs), the main pollutants in e-waste, in loaches was also studied, the mean concentration of total PBDEs in sediment was 6726.17 ng/g wet weight and in water samples was 4.08 ng/L (dissolved phase). BDE 209 was the dominant congener in sediment and with relatively high concentration in water. Relatively low concentration of BDE 209 (less than 0.01% of total PBDEs) and high concentration of BDE47 (up to 39.34% of total PBDEs) were detected in loaches.     

Ecotoxicological effects of mixed pollutants resulted from e-wastes recycling and bioaccumulation of polybrominated diphenyl ethers in Chinese loach (Misgurnus anguillicaudatus)

To understand potential ecotoxicological effects of electrical and electronic equipment waste (e-waste) recycling and polybrominated diphenyl ethers (PBDEs) bioaccumulation in loaches, a semi-field experiment using Chinese loach (Misgurnus anguillicaudatus) as experimental fish was performed. Larval loaches were kept into net-cage for three months in an e-wastes recycling site and a reference site in Southeastern China. There was significant difference of the survival rate between the loaches from the e-wastes recycling site (27%, 19/70) and from reference site (70%, 49/70). Histopathological responses were also found in all the livers examined in loaches from the e-wastes recycling site. These results showed that mixed pollutants resulted from e-wastes recycling led to ecotoxicological effects on loaches. The bioaccumulation of polybrominated diphenyl ethers (PBDEs), the main pollutants in e-waste, in loaches was also studied in this e-wastes recycling site, the mean concentrations of total PBDEs in sediment was 6726.17 ng/g wet weight and in water samples was 4.08 ng/L (dissolved phase). BDE209 was the dominant congener in sediment and with relatively high concentration in water. Relatively low concentration of BDE209 (less than 0.01% of total PBDEs) and high concentration of BDE47 (up to 39.34% of total PBDEs) were detected in loaches.     

沈阳地区地表水、浅层地下水及沿岸土壤中苯

对沈阳地区主要地表水(浑河、细河、蒲河、沈抚灌渠)及其沿岸地下水和土壤中苯系物(BTEX)的污染特点和分布特征进行了研究.结果表明:细河和沈抚灌渠地表水中BTEX检出率较高(33%～67%),苯和甲苯是该区域的主要污染物,ρ(苯)和ρ(甲苯)分别为<0.30～24.90和<0.30～354.00 μg/L;地表水检出的BTEX均未超过《生活饮用水卫生标准》(GB5749—2006)的限值(1 510 μg/L). 细河两岸的浅层地下水在一定程度上受到BTEX的污染,苯和甲苯的检出率分别为25%～33%和13%～25%,二甲苯和乙苯检出率较低(0～20%). 彰驿镇19个监测井中有2个浅层地下水监测井中的ρ(苯)超过GB5749—2006限值(10 μg/L),夏季ρ(苯)最大值为236.00 μg/L. 沿岸附近土壤中5种BTEX全部被检出,检出率均高于相应的河水. 研究区包气带土壤层虽具有良好的防污性能,但也具有储存和阻碍BTEX挥发和降解的负面效应,对当地的生态系统和人类健康构成了潜在的威胁.      

Distribution of polybrominated diphenyl ethers and decabromodiphenylethane in surface sediments from Fuhe River and Baiyangdian Lake, North China

Nineteen surface sediment samples collected from Baiyangdian Lake and its inflowing river (Fuhe River) in North China were analyzed for polybrominated diphenyl ethers (PBDEs) and decabromodiphenylethane (DBDPE). The concentrations of PBDEs and DBDPE in sediments ranged from 5.5 to 300.7 ng/g dry weight (dw) and 1.1 to 68.2 ng/g dw, respectively. Their levels in sediments in Fuhe River were significantly higher than those in Baiyandian Lake. Compared to data from other regions, the PBDE levels in surface sediments from Baiyangdian Lake and Fuhe River were in the medium to lower range. Among the PBDE congeners, BDE209 was predominant, with contributions to the total PBDEs ranging from 79.4% to 97.3% in sediment samples. For the lowly brominated congeners (tri- to hepta-BDE), BDE47 and BDE99 were the most abundant, which contributed 52.1% and 44.1% to the sum of tri- to hepta-BDEs in the sediments from Baiyangdian Lake and Fuhe River, respectively. The compositional patterns of PBDEs in Baiyangdian Lake sediments indicated that technical deca-BDE mixture was the major pollutant sources with a minor contribution of penta-BDE mixture. The present study suggested that the importance of Fuhe River as a possibly potential sources of PBDEs contamination in Baiyangdian Lake.