中国表层水体沉积物中多环芳烃源解析及评价

采用索氏提取气相色谱-质谱法测定中国6个重点水体表层沉积物中16种多环芳烃的含量。各化合物含量范围分别为长江6.20~163 ng/g、淮河7.90~249 ng/g、海河12.1~401 ng/g、松花江5.75~152 ng/g、太湖29.1~2 810 ng/g和滇池19.1~795ng/g；16种多环芳烃的总量分别为：长江1 147 ng/g、淮河1 723 ng/g、海河2 595 ng/g、松花江793 ng/g、太湖12472 ng/g、滇池3 714 ng/g，属中等污染水平。利用特征分子比值法分析结果表明6条水体表层沉积物中PAHs均可能以燃料（包括柴油、汽油、煤、木材）燃烧以及焦化污染为主。淮河和滇池还可能存在轻微石油泄漏污染。利用沉积物质量基准法（SQGs）和沉积物质量标准法分别对6条水体表层沉积物中多环芳烃的风险评估表明严重的多环芳烃生态风险在这些水体表层沉积物中不存在，但长江、淮河、松花江、海河均可能存在一定的潜在风险，负面生物毒性效应会偶尔发生，风险主要来源于荧蒽和菲。太湖和滇池水体中存在的潜在多环芳烃风险种类较多，风险主要来源于菲、荧蒽、芘、苯并（a）蒽、苊和蒽，对水生生物毒性效应较高，有必要进行更深入细致的调查研究高风险区域底栖生物的受损状况、污染来源和途径，以制定合理的污染控制对策。     

商丘市包河表层沉积物中多环芳烃污染初步研究

对包河表层沉积物6个位点的样品中多环芳烃进行了研究,分析其含量、分布特征及其生态风险评价,并结合采样点的情况对其进行源解析,共检测出6种多环芳烃,含量范围为0~9. 50 ng/g。按城市分布情况来看,工业厂附近多环芳烃的含量相对较高。比值法和因子分析法结果显示,多环芳烃污染主要来源于煤炭的燃烧,目前包河表层沉积物中多环芳烃含量处于低风险水平,尚未对生物造成显著的负面影响.     

搬迁化工厂区土壤中多环芳烃污染及来源分析

分析南通某搬迁化工厂区土壤中16种优控多环芳烃（PAHs）污染物的含量特征及污染水平。结果表明，车间和仓库土壤中多环芳烃总量为200—300ng／g，在南通市耕地土壤污染水平范围内。停车场土壤中PAHs含量为3435ng／g，污染水平高于普通耕地，与交通干线两侧土壤相当，土壤中PAHs以4环及4环以上PAHs为主，为汽车尾气污染，若继续用于道路或停车场等功能无需进行PAHs修复。     

固相膜萃取-高效液相色谱法测定地下水中的多环芳烃

采用C18固相膜萃取对地下水中15种多环芳烃进行富集净化，以二氯甲烷作洗脱溶剂，高效液相色谱法，荧光检测器测定。对萃取、浓缩和色谱条件进行优化，在1．ooixg／L～40．0μg／L范围内测定标准系列溶液并绘制标准曲线，相关系数R2〉0．999；15种多环芳烃的仪器检出限为0．4ng／L～3．0ng／L；对地下水样品加标，平均回收率在75．7％～96．7％之间；标准溶液平行测定7次的RSD为3．1％～11．9％。     

淮南市春季大气PM 10 中多环芳烃的污染特征及来源

2008年4月-2008年6月对淮南市的5个采样点PM10连续采样，分析了其中多环芳烃（PAHs）。PAHs质量浓度的最大值和最小值分别为112ng／m^3和15.2ng／m^3，PAHs春季质量浓度均值为40.2ng／m^3；PAHs组成以4环和5环为主；春季不同采样点PAHs质量浓度与环境温度呈负相关关系，运用PAHs比值综合判断，淮南市春季大气PM10中PAHs主要来源于燃煤和机动车尾气。     

南昌市周边农田土壤中多环芳烃的污染特征及来源分析

采集南昌市周边三个县的18个农田表层土壤样品,采用液固萃取-层析净化-高效液相色谱分析技术,研究了土壤中16种优控多环芳烃类物质的含量和组分特征,运用主成分因子荷载方法分析了其污染来源,并初步评价了其风险水平。结果表明,该区域内农田土壤33.3%轻度污染,最高污染样点PAHs含量为422.8ng/g,最低污染样点PAHs含量为75.2ng/g,平均含量为197.9ng/g,且远离城市的农田土壤残留水平明显低于靠近城市的农田土壤;PAHs的组分特征为以毒性水平较低的低环化合物为主;其污染来源主要是煤、天然气和汽油燃烧组成的混合源。     

多环芳烃测定中净化方法的研究

对多环芳烃测定中的净化方法进行研究，为了选出最佳净化柱，在一定条件下分别采用硅胶LC-Si、弗罗里LC-Florisil和C18固相萃取净化柱对一定浓度的多环芳烃标准溶液进行净化，测定吸附后流出液多环芳烃浓度，计算吸附率；测定洗脱后流出液多环芳烃浓度，计算洗脱率。测定结果为硅胶、弗罗里和C18固相萃取净化柱对多环芳烃的吸附率分别在87．1％～100％，99．5％～100％和96．6％～100％之间，洗脱率分别在0～106％，78．7％．109％和79．0％～115％之间。结果表明，GC／MS内标法测定样品中多环芳烃使用最理想的净化柱为弗罗里净化小柱，其次为C18净化小柱，最后为硅胶净化小柱。     

ASE萃取-SPE净化- HPLC法测定土壤中多环芳烃

建立了加速溶剂萃取-固相萃取净化-高效液相色谱测定土壤中16种多环芳烃的方法,优化了试验条件.方法线性关系良好,16种多环芳烃的检出限在0.412 ng/g～3.974 ng/g之间,空白加标试验的相对标准偏差在1.2%～12.7%之间,基质加标回收率在60.4%～126%之间.实际样品的测定结果表明该方法分离效果好,能够满足土壤分析的要求.     

京杭大运河扬州段表层沉积物中多环芳烃的分布及风险评价

采用HPLC定量检出京杭大运河扬州段表层沉积物中16 种优控PAHs 的总量范围在505~4532.2ng/g (干重) 之间,平均值为2359.4ng/g,属中等污染水平,沉积物中的多环芳烃主要来源于煤炭、木材及石油的不完全燃烧;利用沉积物质量基准法(SQGs)对京杭大运河扬州段沉积物中多环芳烃的风险评价表明, 严重的多环芳烃生态风险在京杭大运河扬州段沉积物中不存在,负面生物毒性效应会偶尔发生, 风险主要来源于低环的多环芳烃。     

泰安降水中多环芳烃的浓度分布和来源分析

于2006年4月到2007年8月在泰安市城北设立采样点收集降水样品,对样品中的13种美国环保署(US EPA)优控多环芳烃(PAHs)及NO3-、SO42-等无机阴、阳离子进行了定量分析.测定结果表明,雨水样品中∑13PAHs含量范围在11.3～179.4ng/L之间,平均浓度为89.8ng/L;NO3-、SO42-分别在16.35～186.4ueq/L及53.83～721.9ueq/L之间;样品中无机阴、阳离子总和之比∑(+)/∑(-)的平均值为0.93.相关分析表明,样品中菲、芴、萤蒽等3、4环多环芳烃化合物含量较高;样品中的PAHs浓度与季节存在一定的相关性,但与样品中的NO3-、SO42-浓度间无明显的相关性;样品中的多环芳烃主要来源于煤炭、木材及石油的不完全燃烧.     

Contributions of deposited particles to pine needle polycyclic aromatic hydrocarbons

The contributions of deposited particles (P) to polycyclic aromatic hydrocarbon (PAH) levels in pine (Cedrus deodar) needles sampled from the Dalian region were evaluated by washing off the particles from pine needle surfaces. P values ranged from 4.4 +/- 2.2% for fluorene to 69.9 +/- 4.0% for indeno(1,2,3-cd)pyrene, and positively correlated with the logarithm of octanol-air partition coefficients (log K OA) of each PAH significantly. P and the total levels of 14 PAHs under study ( summation PAHs), that ranged from 490 to 3241 ng g(-1) dw (dry weight) with median value of 1521 ng g(-1) dw, were high for traffic areas, and low for residential or park areas, implying the significant contributions of PAHs in both gas and particle phases emitted by vehicles. However, PAH profiles in pine needles were not significantly altered by the washing, due to the low fractions (2-5%) of the 5- and 6-ring PAHs in summation PAHs. The high wind speed and frequently alternating wind directions in the Dalian spring could quicken the depuration processes of pine needle PAHs. Thus, the local meteorological conditions and source variations should be taken into account when using pine needles to implicate seasonal variations of atmospheric semi-volatile organic compounds.     

Supercritical fluid extraction of polycyclic aromatic hydrocarbons from white pine (Pinus strobus) needles and its implications

A supercritical fluid extraction (SFE) method was developed for the extraction of polycyclic aromatic hydrocarbons (PAHs) from fresh and fallen pine needles. Toluene-modified CO2 was used as the extracting fluid, and the extracted PAHs were analyzed by GC-MS. Using a two-stage extraction procedure, a static extraction at 180 degrees C and a dynamic extraction at 60 degrees C, and an in-cell silica gel plug plus a post-oven silica gel column, the extraction and fractionation of PAHs can be accomplished in one step. Over a seven month period, a significant variation was observed for PAHs in urban samples, while PAHs in mountain samples were at much lower levels (by a factor of approximately 8) and showed little seasonal change. Although dry fallen needles and fresh needles contained similar amounts of PAHs, in the fallen needles the lower molecular weight PAHs were partially lost while the higher molecular weight PAHs were slightly enriched. Pollution in urban areas was found to be highly localized, and buildings and trees are believed to be important factors in the restriction of atmospheric PAHs.     

Distribution and sources of PAHs using three pine species along the Ebro River

Needles of three pine species (Pinus halepensis, Pinus pinea and Pinus nigra) were analysed to assess the occurrence of polycyclic aromatic hydrocarbons (PAHs) in 34 sites located throughout the Ebro River, in Northeast Spain. Overall, the concentration varied between 55 and 808 ng g^− 1 (dry weight). The three- and four-ring PAHs were the most representative, with phenanthrene having 43% of the total PAH load and naphthalene showing a high incidence in rural areas. Despite matrix apparent similarities, P. halepensis needles revealed higher entrapment levels than P. nigra and P. pinea, the latter showing the lowest levels. The assessment of possible sources using PAH ratios (phenanthrene/anthracene and fluoranthene/pyrene) did not reveal a clear tendency regarding the distinction of petrogenic and pyrogenic sources in general, reflecting heterogeneous sources of PAHs in the Ebro area.     

Growth, aboveground biomass, and nutrient concentration of young Scots pine and lodgepole pine in oil shale post-mining landscapes in Estonia

The investigation was carried out in 8-year-old Scots pine (Pinus sylvestris L.) and lodgepole pine (Pinus contorta var. latifolia Engelm.) plantations on post-mining area, Northeast Estonia. The aim of the study was to assess the suitability of lodgepole pine for restoration of degraded lands by comparing the growth, biomass, and nutrient concentration of studied species. The height growth of trees was greater in the Scots pine stand, but the tree aboveground biomass was slightly larger in the lodgepole pine stand. The aboveground biomass allocation to the compartments did not differ significantly between species. The vertical distribution of compartments showed that 43.2% of the Scots pine needles were located in the middle layer of the crown, while 58.5% of the lodgepole pine needles were in the lowest layer of the crown. The largest share of the shoots and stem of both species was allocated to the lowest layer of the crown. For both species, the highest NPK concentrations were found in the?needles and the lowest in the stems. On the basis of the present study results, it can be concluded that the early growth of Scots pine and lodgepole pine on oil shale post-mining landscapes is similar.     

A comparison of the growth of Scots pine (Pinus sylvestris L.) in a reclaimed oil shale post-mining area and in a Calluna site in Estonia

The growth of Scots pine and its suitability for afforestation of post-mining landscapes in Northeast Estonia were assessed in comparative analytical studies by using morphological parameters and mineral nutrition characteristics. The growth and nutrient uptake of Scots pine growing on post-mining substrate were compared with the characteristics of pines of the same age (22–23 years) in a Calluna forest site type predominant in North Estonia in similar climatic zone. Results of the analyses of soil upper layers showed that the concentration of N and P in soil did not differ between the opencast spoil and Calluna site, but significantly higher pH of soil and concentrations of K, Ca, and Mg were found in mine spoil. The concentrations of K and Mg in needles were significantly higher in the post-mining area, but the concentrations of N, P, and Ca did not differ significantly. Comparison of the needle nutrient concentration with the standard for optimum concentrations revealed P deficit in the post-mining area and P and K deficit in the Calluna site. Scots pine formed longer and thinner needles and shoots in the post-mining substrate than in the Calluna site. It was assumed that in the post-mining area the growth of pines is predominantly dependent on K and Ca concentrations in their tissues as the biomass of needles was strongly correlated with the K/Ca ratio, whereas the biomass in the Calluna site was correlated with the N/P ratio. The height and diameter of trees were significantly larger in the post-mining area.     

Monitoring of heavy metals uptake and allocation in Pinus sylvestris organs in alkalised soil

The concentration of heavy metals in soil and in Scots pine (Pinus sylvestris) organs growing on a pH gradient from 4.0 to 7.9 of soil at different distances from a cement plant was monitored. Emission for over 40 years of alkaline dust (pH 12.3-12.6) into the atmosphere in North Estonia had resulted in alkalisation and elevated concentration of total heavy metals in upper layers of the soil (0-30 cm), which was considerable even 10 years after the dust pollution stopped. Monitoring showed that the accumulation and allocation of heavy metals varied between the stem, shoots and needles and differed from the trees in the unpolluted area, depending more on the mobility of elements and the pH than element concentrations in the alkaline soil. A strong negative correlation was found between the soil pH and Mn, Zn and Cd concentrations in different tree organs. Compared to the unpolluted area, Pb was present in relatively higher concentrations in all organs but Cr, Fe and Cu in needles and shoots. The concentrations of Mn and Cd were much lower than control in all organs of trees in alkalised soil. The height increment and density of needles on shoots were predominantly in negative correlation with the pH of soil.     

Dust-particle migration around flotation tailings ponds: pine needles as passive samplers

The potential use of dust particles trapped on Scots pine needles for tracking dust migration around flotation tailings ponds in the Silesian-Krakowian ore district, Southern Poland was tested. 1-, 2- and 3-years old needles were studied using a scanning electron microscope and energy dispersive X-ray microanalysis. Particle sizes and morphologies, and the nature of the compounds hosting metals ions, were examined. A large majority of the particles examined are <10 microm in size. Almost 80% of particles represent respirable dust. All the components in the flotation wastes appear among the chemical compounds identified in particles on the pine needles. The quantity of the waste particles decreases with distance from the flotation tailings ponds. The analysis of dust particles on pine needles could be a useful method for estimating vectors and travel distances of suspended dust migrating around open flotation tailings ponds and around other point sources emitting dust particles with chemical compositions differing from the environmental background.     

Quantitative assessment of polycyclic aromatic hydrocarbons in sewage sludge from wastewater treatment plants in Qingdao, China

In this study, 16 polycyclic aromatic hydrocarbons (PAHs) were detected in sewage sludge samples from four wastewater treatment plants (WWTPs) in Qingdao, China. These WWTPs differ in the type of treatment used and in the origin of the wastewater. The total amounts of PAHs in digested sludges ranged from 1.9645 to 6.5752 mg/kg, which did not exceed the projected European Union cut-off limits (6 mg/kg) for sludge found in farmland, except for the Haibohe WWTP. Significant differences were observed in overall PAH values between WWTPs receiving domestic effluents and those receiving industrial effluents. The total amounts of PAHs in digested sludge from the Licunhe and Haibohe WWTPs, which mainly received industrial effluents, were markedly higher than those of the Tuandao and Huangdao WWTPs, which received only domestic effluents. The distribution of PAH compounds in digested sludges were analysed. At the Tuandao, Huangdao and Licunhe WWTPs, 2-, 3-, 4-benzene rings were predominant, accounting for 100%, 99.8% and 99.0% of the sum concentration of 16 PAHs (∑PAHs), respectively. At the Haibohe WWTP, a large number of high molecular weight PAHs (5-, 6-benzene rings) were observed, accounting for 30% of the ∑PAHs. The sum of seven carcinogenic PAHs (∑PAHs-c) ranged from 0.8694 to 3.0389 mg/kg in four WWTPs. The highest value was found in the Haibohe WWTP. Moreover, the PAH concentrations in sludges from the different treatment processes in the Licunhe and Tuandao WWTPs are discussed.     

Detection of sulphur dioxide in the air using Scotch pine needles

Air quality is especially important in surface layers, for it is this layer that provides the living components of environment with the needed oxygen and carbon dioxide. Various air polluting gases penetrate cells affecting and contaminating them. Chloroplast shell of some pine species, for instance, doubles under the impact of carbon dioxide which is followed by tillacoids swelling and reduction.Literature provides opinions of some authors, who consider Scotch pine needle to be a biological indicator of sulphur dioxide. Others object to it basing on the observations of physiological development.The property of a Scotch pine as that of biological indicator manifests in SO₂ absorption by its needles. The analysis of total content of SO₂ in the needles shows an increase of SO₂ concentration.Sulphur in the needles is found in the form of organically bound sulphur, aminoacids, hormones as well as in the form of sulphates.Basing on our previous analysis we have generalized the data on the correlation concentrations of sulphur dioxide in the air and general concentrations of sulphur in the needles. We have supplemented the observations with the analyses of organically bound sulphur and concentrations of nonorganic sulphur. According to research data, needles contain a characteristic and rather stable quantity of organically bound sulphur.So we may state that the SO _inf4 ^sup2– concentration and the amount of SO₂ absorbed from the air are interdependent.Some authors state that SO _inf4 ^sup2– content in the soil doesn't affect sulphur content in pine needles. That is why we studied the affect of SO _inf4 ^sup2– content in the soil on sulphur content in Scotch pine needles.We could prove this statement by means of various kinds of analyses only partially. The ion transport is affected by the presence of other ions, pH and a lot of other factors.What may be said for sure is that different qualities of soils gave only minor and insignificant deviations.Hence our assumption about the SO₂ contamination from air, proved by its effect on the soils, turns to suit approximate measurements.     

Trends in background levels of persistent organic pollutants at Kosetice observatory, Czech Republic.2) Part II. Aquatic and terrestrial environments 1996-2005

A multimedia sampling of ambient air, wet deposition, surface water, sediment, soil and biota has been performed at Kosetice background observatory in the southern Czech Republic since 1988. An integrated monitoring approach was applied to assess the current state, anthropogenic impacts, and possible future changes of terrestrial and freshwater environments. Average PCB concentrations in the individual matrices calculated from ten years of sampling on multiple sites varied between 2 ng g(-1) in sediment and 7 ng g(-1) in soil or moss. DDT concentrations were lower in moss and needles (2 ng g(-1) and 4 ng g(-1), respectively) than in sediment (11 ng g(-1)) and soil (20 ng g(-1)), while the HCH level was higher in moss and needles (5 ng g(-1) and 6 ng g(-1), respectively) than in soil or sediment (1 ng g(-1) and 2 ng g(-1), respectively). The highest average level of PAHs was found in soil (600 ng g(-1)), while it was lower in needles (230 ng g(-1)), moss (210 ng g(-1)) or sediment (210 ng g(-1)). Time related trends of concentration levels of persistent organic pollutants in all matrices were investigated. Moss and needle trend patterns resembled those of the ambient air, showing a slight concentration decrease of all compounds, except for hexachlorobenzene. The soil, water and sediment concentrations showed a similar decrease of PAHs, PCBs, and HCHs, but there was no clear trend for DDTs and HCB.