土壤和沉积物中的聚合有机质对多环芳烃分布和提取的影响

为了研究土壤和沉积物中凝聚型有机碳(碳黑、干酪根)的含量及其对多环芳烃(PAHs)分布和提取的影响,分别用三氟醋酸(TFA)和在375℃下通氧燃烧的方法从珠江三角洲2个污染土壤和5个河口沉积物样品中提取酸非水解有机碳(NHC)和碳黑(BC);用索氏抽提法和不同溶剂的加速溶剂萃取法(包括连续加速萃取法ASESum和标准溶剂萃取法ASESTD)抽提土壤和沉积物中的多环芳烃,并在不同温度梯度(25℃到150℃)下用水为溶剂加速溶剂萃取其水溶态.结果表明,1)NHC是珠江三角洲土壤和沉积物中总有机碳的重要组成部分,NHC碳明显高于BC碳,NHC和BC分别占土壤和沉积物中有机碳的25.6%￣73.8%和4.64%￣17.3%.2)3种有机溶剂(丙酮、甲苯1、甲苯2)连续抽提的PAHs含量是索氏抽提的2.11倍;5种ASE方法(丙酮、甲苯1、甲苯2、ASESum、ASESTD)提取的PAHs含量与NHC含量存在明显的相关性,而且比PAHs含量与BC或无定型有机碳(AOC)含量的相关性更明显.3)在不同温度梯度下水溶态PAHs浓度符合Van’tHoff方程.研究说明除了BC外,非水解有机碳对土壤和沉积物中PAHs的分布和提取具有重要影响.     

生活垃圾堆填区周边农田土壤中多环芳烃的污染特征

土壤多环芳烃(PAHs)的污染日益受到关注,PAHs是垃圾渗滤液中的主要有害成分之一.以苏北某市城郊结合部露天垃圾堆放场为对象,采用高效液相色谱法分析周边农田土壤中16种PAHs的含量特征及分布规律.结果表明,垃圾场周边农田土壤PAHs含量总体表现为随距垃圾堆体的距离增大而降低的趋势.土壤中PAHs总量(平均值为1 208.5μg·kg-1)明显高于未污染土壤(509.25μg·kg-1),其中显著提高了土壤中难降解、难挥发的4环芳烃的含量,按照欧洲农业土壤PAHs含量与分布标准,达到中等或中等以上PAHs污染水平,说明垃圾堆填场周边农田土壤存在PAHs的污染风险.     

几种多环芳烃在不同类型稻田土壤中的降解行为

为揭示我国不同类型稻田土壤中多环芳烃(PAHs)的降解率,采集了8个地区的稻田土壤,分别加入菲、荧蒽和苯并[a]蒽进行室内培养试验,分析不同类型稻田土壤中PAHs降解速率的差异及其与土壤理化性质的关系。结果表明,不同类型稻田土壤中PAHs降解能力由大到小依次为四川石灰性紫色土、黑龙江黑土、重庆中性紫色土、山西褐土、北京潮土、安徽黄褐土、河南潮土和湖南黄壤。不同类型稻田土壤中PAHs降解率在培养7 d时均可达51.5%,28 d后降解率大于80%。土壤中PAHs易降解程度由高到低依次为菲、荧蒽和苯并[a]蒽。除四川石灰性紫色土和重庆中性紫色土外,PAHs能显著增加其他类型土壤中总细菌数量和菲降解过程中的双加氧酶功能基因phnAc数量。冗余分析结果表明,土壤中菲和荧蒽降解速率与土壤中NH_4~+-N和有机质含量呈显著正相关(P0.05),与pH值和含水量呈负相关。土壤中苯并[a]蒽降解速率与土壤理化性质均无显著相关性(P0.05)。不同类型稻田土壤中PAHs自然降解速率和留存时间有所差异,可通过在土壤中添加氮肥等营养物质促进PAHs的降解。     

珠江三角洲表层土壤中的多环芳烃

多环芳烃是一类主要由人类活动排放的有毒有机污染化合物,对人和生物体具有致癌、致畸和致突变效应,是评价土壤生态污染的重要内容之一。文章利用螺旋钻采样、索氏抽提、硅胶氧化铝净化和GC-MS分析,研究了珠江三角洲不同功能区(城市点、郊区点、乡村点)的76个表层土壤样品(耕作土、非耕作土)中多环芳烃(PAHs)的含量、分布特征及其影响因素。结果表明,16种优控PAHs的总质量分数范围为31.5~791.6ng·g-1(平均279.1ng·g-1,以干质量计),以萘(44.4%)、菲(13.7%)、荧蒽(8.4%)、芘(4.9%)、■(6.6%)等化合物为主。与国内外其它地区的城市相比较,珠江三角洲地区土壤PAHs的污染程度较低,在组成上也表现出亚热带地区独特的中、低环化合物为主的特征。受人类经济活动的影响,地处珠江三角洲中部的经济工业中心地带,土壤中PAHs含量相对较高。珠三角表层土壤PAHs含量和组成分布主要受大气沉降控制,而与土壤有机碳、pH的相关性较小。高温潮湿的亚热带季风气候是影响珠三角土壤PAHs的降解和迁移的重要环境因素。     

深圳表层土壤中多环芳烃的污染特征及来源

2007年1月采集深圳市36个土壤,采用气相色谱-质谱仪对其中的16种优先控制的多环芳烃(PAHs)进行分析.结果表明:16种PAHs的含量范围在67.77137.0 ng · g-1之间,平均值为664.7 ng · g-1,其中苯并[b]荧蒽的含量最高,致癌性PAHs占总量的51.9﹪.PAHs在深圳不同土地利用类型的土壤中的含量由高到低的次序为:菜园地,城区,果园地,林地.PAHs主要来源于燃烧来源,果园地、林地中的PAHs主要来源于长距离的大气迁移,部分城区土壤指示有石油来源.深圳市19.4﹪的土壤属重污染,重污染的土壤主要分布在菜园地和城区两类土壤中,城区表层土壤PAHs含量较国外其他城市低.结果对于认识PAHs在深圳土壤中的分布规律和环境迁移、以及如何控制PAHs污染具有重要的意义.     

我国表层土壤多环芳烃含量的空间分布及成因

为全面了解我国表层土壤多环芳烃(PAHs)含量状况及空间分布,收集整理了1999—2018年发表的208篇有关全国各地表层土壤PAHs的文献,综合运用ArcGIS空间插值技术、地理探测器模型和统计学方法,定量分析了我国表层土壤PAHs含量、空间分布、主要来源及成因。结果表明:我国各地表土PAHs平均含量的空间分布具有明显的区域特征,从华北、东北、华东、中南、西北到西南地区依次递减,华北地区土壤∑16PAHs平均含量约为西南地区的2. 5倍;我国土壤PAHs含量总体上处于中低污染水平,中等污染、轻微污染和未污染土壤占比分别约为22. 6%、71. 1%和6. 3%。利用地理探测器对9种社会经济影响因素的定量分析表明,燃煤发电对PAHs含量的空间分布格局影响显著高于其他因子;主成分分析结果也表明燃煤是重要污染源之一。该研究对实现我国土壤PAHs的科学管控和防治具有一定参考价值。     

天津污灌区耕作土壤中多环芳烃的纵向分布

研究了天津污灌区土壤剖面中多环芳烃含量的分布特征，几个代表性样点的研究表明，天津市郊水稻田中PAHs含量最高，菜地含量居次，高粱地含量最低。PAHs总含量在土壤剖面的纵向分布总体上是随着土壤剖面的加深而降低。由于长期污水的淹灌作用，水稻田中PAHs含量出现了局部异常高值。用萘(Nap)、菲(Phe)和苯并[a]芘(Bap)作为高低环组分的代表物质分析PAHs在土壤剖面的分布规律，发现Nap、Phe和Bap的含量在纵向剖面上变化趋势基本相同，总体上含量随着剖面的加深而降低。比较单个组分含量在土壤剖面中的变化，在犁底层以下，Bap的含量基本上低于检测限，而Nap的含量在整个土壤剖面中均高于Bap。PAHs含量在土壤剖面上的分布主要受其物理化学性质、土壤中有机碳和粘粒含量的影响。     

不同焦化厂土壤中多环芳烃污染特征比较研究

为研究焦化生产对土壤多环芳烃(PAHs)污染规律,采集北京、重庆和太原地区3个焦化厂地块的土壤样品共1 437个,采用气相色谱-质谱(GC-MS)法测定US EPA优先控制的16种PAHs质量含量。结果表明,北京、重庆和太原地区3个焦化厂污染土壤中总多环芳烃(ΣPAHs)质量含量最大值分别为10 647.2、39 332.7和19 381.9 mg·kg~(-1),PAHs污染都很严重,其中5环PAHs对ΣPAHs毒性的贡献率最大(63.01%～78.61%)。在垂直方向上,GB 36600—2018《土壤环境质量建设用地土壤风险管控标准》中8种优先管控的PAHs质量含量最大值随着土壤深度的增加而降低,其中,重庆场地土壤中污染物质量含量最大值随着土壤深度增加而减少的降低速率明显低于其他2个场地。同分异构比值法分析结果表明,北京、重庆和太原地区3个焦化厂来源于煤炭燃烧的PAHs占比分别为88.46%～90.38%、83.56%～98.17%和74.56%～92.96%,焦化厂土壤中PAHs仍存在少部分石油泄露、燃烧等污染源。北京、重庆和太原场地8种PAHs超过GB 36600—2018一类、二类管制值的最大比例分别为8.23%、5.18%,15.34%、9.77%及13.72%、8.68%,北京和重庆某焦化厂土壤再开发利用的健康风险更高。研究显示,在0～20 m深度,焦化厂搬迁后其旧址的土壤中依然残留着较高质量含量PAHs,环境风险较高。相似焦化厂场地土壤中PAHs污染特征与其所在区域以及土壤地层分布差异密切相关,地层分布在很大程度上会影响PAHs在土壤中的赋存和迁移,且对高环PAHs的影响相对于低环PAHs较小。该文研究结果可为焦化工业不同污染场所的土壤修复和环境风险评估提供参考。     

强化生物堆法修复多环芳烃污染土壤的初步研究

以多环芳烃(PAHs)污染场地土壤为研究对象,研究了不同工艺条件的生物堆反应器中PAHs降解效果,并通过对PAHs高效降解混菌的筛选富集,探讨菌液投加对生物堆技术处理PAHs污染土壤的强化修复作用效能。结果表明,生物堆运行过程中土壤pH和含水率基本保持稳定,总PAHs在9 d内快速降解,降解率达到80%以上,之后基本不变;生物堆在短期内(9 d)对低分子质量(2～3环)PAHs具有较高降解效率,达到91%;但中、高分子质量(4～6环)PAHs的降解效率只有60%,降解中、高分子质量PAHs可能需要更长时间。在试验期内添加表面活性剂、通风和投加PAHs降解菌液对总PAHs降解率均没有显著提升,但添加菌液后土壤脱氢酶活性大幅升高,投加菌液的3#和4#处理在80 d时脱氢酶活性较41 d时分别增加约7倍和9倍。PAHs降解菌液可能对PAHs降解中间产物的进一步矿化起到显著促进作用。添加表面活性剂并通风处理的脱氢酶活性更高,达到10 740μg·g~(-1)·h~(-1),说明其对中间产物降解的促进作用更大。该研究验证了生物堆技术在PAHs污染土壤修复中的有效性,并对比了不同强化措施对修复效果的影响,为该技术在PAHs污染场地修复中的应用提供了重要数据支撑。     

焦化厂污染场地表层土壤有机-矿质复合体中多环芳烃的分布

采用湿法物理分级方法将湖南省某焦化厂遗留场地表层土壤分成4种粒级的有机-矿质复合体组分,即粘粒(<2μm)、粉粒(2—20μm)、细砂(20—200μm)和粗砂(>200μm),并研究了美国EPA优先控制的16种多环芳烃(PAHs)在其中的分布特征及土壤不同有机-矿质复合体组分中有机质和矿物质组成的差异对PAHs赋存分布的影响.研究结果表明,不同粒级有机-矿质复合体中PAHs的含量顺序为粗砂>粉粒>细砂>粘粒,低环PAHs(环数≤3)在粘粒中的含量较高,达到56.3%,而高环PAHs(环数≥4)在粉粒、细砂和粗砂中的分布较高含量分别是79.37%、72.7%和71.63%,各粒级矿质复合体中PAHs含量与土壤有机碳有较好的相关性.通过对有机-矿质复合体进行X射线衍射分析发现,场地土壤粘粒和粉粒中粘土矿物含量较高,这也在一定程度上影响了污染物质在其中的分布.     

土壤多环芳烃污染根际修复研究进展

多环芳烃(polycyclicaromatichydrocarbons,PAHs)是环境中普遍存在的具有代表性的一类重要持久性有机污染物,具“三致性”、难降解性,在土壤环境中不断积累,严重危害着土壤的生产和生态功能、农产品质量和人类健康。修复土壤多环芳烃污染已成为研究的焦点。根际修复是利用植物-微生物和根际环境降解有机污染物的复合生物修复技术,是目前最具潜力的土壤生物修复技术之一。对国内外学者近年来在土壤多环芳烃污染根际修复的效果、根际修复机理和根际修复的影响因素方面的研究进展作了较系统的综述,并分别分析了单作体系、混作体系、多进程根际修复系统和接种植物生长促进菌根际修复系统对土壤多环芳烃的修复效果。指出根际环境对PAHs的修复主要有3种机制:根系直接吸收和代谢PAHs;植物根系释放酶和分泌物去除PAHs,增加根际微生物数量,提高其活性,强化微生物群体降解PAHs。并讨论了影响根际修复PAHs的环境因素如植物、土壤类型、PAHs理化性质、菌根真菌以及表面活性剂等。植物-表面活性剂结合的根际修复技术、PAHs胁迫下根际的动态调节过程、运用分子生物学技术并结合植物根分泌物的特异性筛选高效修复植物以及植物富集的PAHs代谢产物进行跟踪与风险评价将成为未来研究的主流。     

Dissipation of polycyclic aromatic hydrocarbons and microbial activity in a field soil planted with perennial ryegrass

Dissipation and plant uptake of polycyclic aromatic hydrocarbons (PAHs) in contaminated agricultural soil planted with perennial ryegrass were investigated in a field experiment. After two seasons of grass cultivation the mean concentration of 12 PAHs in soil decreased by 23.4% compared with the initial soil. The 3-, 4-, 5-, and 6-ring PAHs were dissipated by 30.9%, 25.5%, 21.2%, and 16.3% from the soil, respectively. Ryegrass shoots accumulated about 280 ??g·kg^?1, shoot dry matter biomass reached 2.48 × 10⁴ kg·ha^?1, and plant uptake accounted for about 0.99% of the decrease in PAHs in the soil. Significantly higher soil enzyme activities and microbial community functional diversity were observed in planted soil than that in the unplanted control. The results suggest that planting ryegrass may promote the dissipation of PAHs in long-term contaminated agricultural soil, and plant-promoted microbial degradation may be a main mechanism of phytoremediation.     

Polyzyklische aromatische Kohlenwasserstoffe aus diffusen Quellen

Goal and Scope

Polycyclic aromatic hydrocarbons (PAHs) are one group of persistent organic pollutants which are ubiquitous distributed in soils, even in rural areas. After their release into the atmosphere, transportation and deposition, they tend to accumulate in topsoils and sediments. Similar distribution pattern of PAHs in atmospheric deposition, soil samples as well as sediment samples indicate a close relationship between atmospheric input and accumulation of PAHs in the terrestrial environment. The intention of this paper was to estimate the time when precautionary values of the German law of soil protection will be exceeded in rural areas. Furthermore, current soil concentrations will be linked to the historical record of PAHs by means of enrichment factors.

Methods

The historical record of the atmospheric deposition rates of PAHs can be obtained from investigation of sediment cores. Based thereon, enrichment factors of PAHs in the environment were calculated. With these enrichment factors it was possible to estimate the recent PAH concentration in soils in rural areas from currently measured annual deposition rates. Furthermore, concentrations of PAHs in soils and deposition rates can be used to calculate the time when precautionary values will be reached.

Results and Conclusion

PAH deposition rates have been decreasing since about 1960 by a factor of 2–3, but stabilized during the last decade on a level high above pre-industrial time. Thus, further enrichment of PAH in topsoils has to be expected. Actual deposition rates in connection with historical enrichment factors allow to determine the median concentrations of PAHs in rural soils. The time when precautionary values will be reached was calculated to about 300 Years.

Outlook

The database to predict the further development of atmospheric deposition rates is very weak. There was a lack of validated methods concerning direct measurements of atmospheric POP deposition. Meanwhile, a national draft of a standard base on time-integrated passive sampling exists. This method can be implemented to establish a combined soil and deposition-monitoring program in order to assess the risk of further accumulation of POPs in soils.     

Distribution pattern of polycyclic aromatic hydrocarbons in particle-size fractions of coking plant soils from different depth

The concentrations of 16 priority polycyclic aromatic hydrocarbons (PAHs) in four size fractions (<2, 2–20, 20–200, >200 μm) in soils at different depth from a heavily contaminated crude benzol production facility of a coking plant were determined using GC–MS. Vertically, elevated total PAHs concentrations were observed in the soils at 3.0–4.5 m (layer B) and 6.0–7.5 m (layer C), relatively lower at 1.5–3.0 m (layer A) and 10.5–12.0 m (layer D). At all sampling sites, the silt (2–20 μm) contained the highest PAHs concentration (ranged from 726 to 2,711 mg/kg). Despite the substantial change in PAHs concentrations in soils with different particle sizes and lithologies, PAHs composition was similarly dominated by 2–3 ring species (86.5–98.3 %), including acenaphthene, fluorene, and phenanthrene. For the contribution of PAHs mass in each fraction to the bulk soil, the 20–200 μm size fraction had the greatest accumulation of PAHs in loamy sand layers at 1.0–7.5 m, increasing with depth; while in deeper sand layer at 10.5–12.0 m, the >200 μm size fraction showed highest percentages and contributed 81 % of total PAHs mass. For individual PAH distribution, the 2–3 ring PAHs were highly concentrated in the small size fraction (<2 and 2–20 μm); the 4–6 ring PAHs showed the highest concentrations in the 2–20 μm size fraction, increasing with depth. The distribution of PAHs was primarily determined by the sorption on soil organic matter and the characteristics of PAHs. This research should have significant contribution to PAH migration study and remediation design for PAHs-contaminated sites.     

Phylogenetic analysis of hyperaccumulator plant species for heavy metals and polycyclic aromatic hydrocarbons

Increasing concentration of heavy metals (HMs) and polycyclic aromatic hydrocarbons (PAHs) in the soil may impose a serious threat to living organisms due to their toxicity and the ability to accumulate in plant tissues. The present review focuses on the phylogenetic relationships, sources, biotransformation and accumulation potential of hyperaccumulators for the priority HMs and PAHs. This review provides an opportunity to reveal the role of hyperaccumulators in removal of HMs and PAHs from soils, to understand the relationships between pollutants and their influence on the environment and to find potential plant species for soil remediation. The phylogenetic analysis results showed that the hyperaccumulators of some chemicals (Co, Cu, Mn, Ni, Zn, Cd) are clustered on the evolutionary tree and that the ability to hyperaccumulate different pollutants can be correlated either positively (Cd–Zn, Pb–Zn, Co–Cu, Cd–Pb) or negatively (Cu–PAHs, Co–Cd, Co–PAHs, Ni–PAHs, Cu–Ni, Mn–PAHs). Further research needs to be extended on the focus of commercializing the techniques including the native hyperaccumulators to remediate the highly contaminated soils.

     

Spatial distribution of PAHs in a contaminated valley in Southeast China

A survey was conducted on the accumulation and spatial distribution of PAHs in surface soils under different land use patterns in a valley in the Yangtze Delta region with an area of 10 km² containing 15 small copper- and zinc-smelting furnaces. Sixty-five topsoil (0–20 cm) samples were collected and 16 PAHs were determined. The average amount of all the 16 PAHs ranged from 0 to 530 μg kg⁻¹ (oven dry basis), with a mean concentration of 33.2 μg kg⁻¹. Benzo[a]pyrene and indeno[1, 2, 3, -cd]pyrene were the two main PAHs present at high concentrations, while pyrene and fluorene had very low concentrations. PAH concentrations were higher in uncultivated than in cultivated soils, and areas of woods and shrubbery had the␣lowest soil PAH contents. The average PAH-homologue concentrations ranked as follows: 5-rings >> 3-rings, 4-rings > 6-rings >2-rings. Much higher concentrations of PAHs were found in the southern part of the sampling area, perhaps due to deposition of airborne particles by the southeasterly winds in winter and spring. We conclude that the small smelting furnaces were the dominant source of PAHs that accumulated in the soils and the southeasterly winds led to the spatial distribution of PAHs in the topsoils. Land vegetation cover and soil utilization patterns also affected the accumulation and distribution of soil PAHs.     

北京市某废弃焦化厂不同车间土壤中多环芳烃（PAHs）的分布特征及风险评价

以北京市某废弃焦化厂为研究对象,系统采集了6个车间0～4m深的26个土壤样本,利用GC/MS检测了U.S.EPA优控的16种多环芳烃(PAHs)的含量,分析了PAHs在焦化厂不同车间表层土壤的污染状况和深层土壤中的垂直分布特征并对土壤污染风险进行了评估.结果表明,1)该废弃焦化厂不同车间表层土壤(0～20cm)总PAHs(∑PAHs)的残留量介于672.8～144814.3ng·g-1之间;污染程度排序为:回收车间>老粗苯车间>焦油车间>炼焦车间>水处理车间>制气车间.2)该厂未受扰动的土壤样品显示PAHs主要聚集在表层土壤,并随着土壤深度的增加而迅速减少;其他样点由于土壤扰动,∑PAHs含量最大值出现在第三层土壤(80～180cm);该厂4m深底层土壤仍有高浓度PAHs,∑PAHs含量最高值出现在炼焦车间,达12953.1ng·g-1.3)焦化厂土壤PAHs污染主要集中在3环和4环的PAHs单体上,分别占到污染总量的51.3%和31.7%.4)根据Maliszewska-Kordybach的PAHs总量标准及加拿大土壤PAHs单体治理标准,该厂回收、老粗苯、焦油和炼焦车间表层和深层土壤PAHs含量均达到重污染水平,并对其周围土地带来较大风险,需要治理.     

汕头经济特区土壤中优控多环芳烃的分布

运用气相色谱-质谱方法对汕头经济特区131个土样中的美国EPA优控多环芳烃(PAHs)进行定性、定量测定,讨论了PAHs的分布特征。结果表明,该区表层土壤中优控PAHs的总质量分数范围从22.1 ng/g到1256.9 ng/g之间,平均质量分数为(317.3210.2) ng/g。其分布随采样点的位置不同而有显著变化:工业区附近多环芳烃的质量分数最高,城市中心次之,郊区最低。大多数样点中?PAHs质量分数和单种PAH质量分数都呈现w(5~20 cm)> w(0~5 cm)>w(20~40 cm)>w(40~100 cm)的垂直分布规律。该区土壤PAHs以3环和4环化合物为主,单种PAH以萘、菲和苯并[b]萤蒽为主。     

宝天曼木本植物群落数量排序与环境解释

研究选取14个分别代表植被群落、地形因子、土壤因子的指标,利用宝天曼自然保护区32块样地资料,研究了物种分布与环境之间关系。采用DCCA法可将该地区木本植物群落划分为3个类型;物种与9个环境因子之间存在显著的相关关系,前4轴可解释物种总变异的94.1%;海拔、坡度、土壤含水量、坡向是影响该地区物种分布的主要因子,其中海拔是指示物种分布变化的最敏感因子。不同指标集团的典型相关分析结果表明：地形与植被因子之间、土壤因子与植被因子之间第1对典范相关系数分别为0.712和0.783,存在着显著的相关关系,影响植被特征的最重要地形因子是海拔和坡度,土壤因子为土壤厚度和土壤含水量,而对地形和土壤反应最敏感的植被指标分别为林分密度和平均树高,群落分布状态是由地形和土壤因子共同作用所控制的。