液液萃取对邻苯二甲酸酯单体稳定碳同位素比值分馏的影响初探

邻苯二甲酸酯(PAEs)是地下水中主要的有机污染物,其单体的稳定碳同位素比值变化特征有望作为其溯源与过程示踪的依据,为更好地控制其对环境的污染提供可靠的信息.研究表明,在样品前处理过程中涉及一些物理变化过程,有机污染物的稳定碳同位素分馏效应不明显.本文应用液液萃取对样品进行前处理,气相色谱-同位素比值质谱联用法( GC - IRMS)测定地下水中5种邻苯二甲酸酯单体,包括邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸二异丁酯(DIBP)的稳定碳同位素比值,探讨PAEs在液液萃取过程中5种单体稳定碳同位素比值分馏情况.分析结果表明,萃取前后PAEs的碳同位素比值没有显著的变化,说明液液萃取可以作为GC - IRMS测定邻苯二甲酸酯单体稳定碳同位素比值的前期预处理方法.     

广州地区蔬菜生产基地有机污染物含量状况及分布

为了解广州地区蔬菜基地有机污染物的分布情况,选取了6个代表性基地进行调查采样,测试分析了表层土壤、蔬菜及灌溉水中15种邻苯二甲酸酯(PAEs)化合物、16种多环芳烃(PAHs)化合物和19种有机氯农药(OCPs)化合物的质量分数及质量浓度.结果表明:在15种PAEs化合物的总质量分数(w(ΣPAEs))中,土壤样品为158.0~4 321.0 ng/g,蔬菜样品为1 134.0~48 576.0 ng/g;水样中15种PAEs化合物的总质量浓度(ρ(ΣPAEs))为632.0~14 271.0 ng/L;就单个化合物而言,以DiBP、DBP、DEHP三种污染物为主,其三项之和占所有PAEs质量分数的97.5%~99.1%;在16种PAHs化合物的总质量分数(w(ΣPAHs))中,土壤样品为28.48~1 121.96 ng/g,蔬菜样品为238.09~1 000.61 ng/g;水样中16种PAHs化合物的总质量浓度(ρ(ΣPAHs))为338.21~1 239.78 ng/L;在19种OCPs化合物的总质量分数(w(ΣOCPs))中,土壤为0.04~71.28 ng/g,蔬菜为1.08~9.18 ng/g.总体上看,各基地土壤中DBP质量分数均超标,多环芳烃类在灵山、花东、黄埔菜地土壤中存在轻微污染,有机氯农药均未出现污染.     

Occurrence of phthalate esters around the major plastic industrial area in southern Taiwan

The increasing usage and disposal of plastic products could cause the wide distribution of phthalate esters (PAEs) in various environmental media. In this study, six PAE compounds, namely dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, benzyl butyl phthalate, di(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate, were analyzed in various samples collected from the major plastic industrial area of southern Taiwan, including soil, fertilizer and plastic products, for the purposes of identifying of the possible sources of PAEs and assessing the related health risk. The results show that PAEs in soil samples was dominated by DEHP, with the total concentrations in the range of 0.7?±?0.5, 0.2?±?0.1, and 0.3?±?0.2 mg kg^?1 for soil samples from farmland, household back gardens and the roadside, respectively. Contents of PAEs in chemical fertilizer (ND—0 0.87 mg kg^?1) were higher than that in organic fertilizer (ND—0.08 mg kg^?1), and PAEs concentrations (ND—316 mg kg^?1) in plastic mulching films were much less than those in the other types of plastic products (ND—1719 mg kg^?1), implying that major sources of PAEs in agricultural soil could be the use of chemical fertilizer and plastic products other than plastic mulching films. Health risk assessment suggested that, via the exposure to PAEs in soil, the potential non-cancer and carcinogenic risks for adults and children are minimal in most cases, except that a “moderate” carcinogenic risk for children exposure to DEHP. The results of this study can serve as a reference for further pollution prevention and environmental protection plans in relation to the industrial operation and discharge as well as the farming practices.     

超声波萃取-高效液相色谱法测定土壤中邻苯二甲酸酯

邻苯二甲酸酯类(PAEs)是环境激素类物质中的一类化合物。文章对土壤中6种被美国EPA列入"优先监测污染物名单"的PAEs类物质邻苯二甲酸二甲酯(DMP)、二乙酯(DEP)、二丁酯(DBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、二辛酯(DOP)、丁基苄基酯(BBP)邻苯二甲酸酯经超声波萃取、柱层析净化后,采用高效液相色谱法测定。对影响加标回收率的实验条件如萃取溶剂比例、萃取时间和萃取溶剂的选择等进行优化。方法回收率为94.1%～108.2%,相对标准偏差(RSD,n=7)为0.70%～2.42%,方法检出限为0.003～0.009μg/g。建立的方法样品前处理简单、快速,溶剂用量少,液相色谱法分析6种PAEs类物质仅用10 min,适用于大批量土壤样品中PAEs类物质的测定。     

岩溶高原区农业地膜中邻苯二甲酸二乙基己酯的释放及其对覆膜土壤的影响

随着邻苯二甲酸酯类(PAEs)增塑剂在塑料大棚、地膜覆盖栽培技术中的广泛应用,我国农业土壤中已普遍存在邻苯二甲酸二乙基己酯(DEHP)污染问题。针对我国中西部岩溶高原区农业土壤中存在的DEHP环境问题,本文选取云南岩溶高原区的红壤及烟草地膜作为研究对象,通过田间试验模拟覆膜土壤环境,并采用气相色谱-质谱分析法检测农膜、土壤介质中DEHP含量,定量研究了地膜中DEHP的释放及其在覆膜土壤中的浓度分布特征。结果表明:覆盖于原状土壤上的地膜,其DEHP释放量最大,均值为13.57mg/kg;覆盖于加生物抑制剂土壤上的地膜,其DEHP释放量略高于未覆土壤地膜,前者DEHP平均值为10.83mg/kg,后者为10.77mg/kg;地膜中DEHP的释放表现为缓慢释放和集中陡升两个释放段,总体释放量随时间的延长而增加。两组覆膜土壤中DEHP的检出浓度范围分别为0.17～3.74mg/kg(原状土)、0.34～4.29mg/kg(加生物抑制剂土壤),在国内外覆膜农田土壤PAEs类化合物检出浓度范围内;土壤中DEHP含量具有随时间呈先增后减的变化规律。相关性分析表明土壤中DEHP主要来自于地膜中DEHP的释放。研究认为在短周期内岩溶高原红壤不会出现DEHP的累积,合理安排农作物的覆膜种植可有效削减土壤的有机污染。     

气相色谱-质谱法快速测定罗氏海盘车中6种邻苯二甲酸酯类有机污染物

建立了气相色谱-质谱联用技术(GC-MS)测定罗氏海盘车中6种邻苯二甲酸酯类化合物(PAEs)的方法,采用丙酮-正己烷混合溶剂超声提取,通过中性氧化铝和弗罗里硅土填装层析柱净化样品,选用HP-5MS毛细色谱柱分离,选择离子监测模式(SIM)进行定性定量。该方法能同时分离测定罗氏海盘车中邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二正丁酯、邻苯二甲酸丁基苄酯、邻苯二甲酸二(2-乙基己基)酯、邻苯二甲酸二正辛酯等6种邻苯二甲酸酯类化合物。在优化条件下,方法标准曲线的相关系数为0.9975～0.9996,回收率为80.30%～119.00%,精密度(RSD,n=7)为2.2%～5.7%,方法最低检出限为10.00 ng/g。运用建立的方法对罗氏海盘车样品进行分析,检测出罗氏海盘车中含有邻苯二甲酸二异丁酯、邻苯二甲酸二正丁酯、邻苯二甲酸二(2-乙基己基)酯3种污染物,3种污染物含量均低于欧盟的限量标准,同时远低于其他各类食品中的检出含量,样品中邻苯二甲酸二(2-乙基己基)酯平均含量偏高。本法具有高的选择性、灵敏度和准确度,适用于罗氏海盘车中痕量PAEs的测定,为保护海洋环境及海洋资源开发提供技术支持。     

Rare earth elements of the Altar Desert dune and coastal sands, Northwestern Mexico

Twenty-one surficial sand samples from the Altar Desert coastal and desert dune systems were analysed for rare earth elements (REE) content. This was done to observe the provenance signatures for four strategic dune localities near the Colorado River Delta, the El Pinacate dune fields, and the beaches of the north of the Gulf of California in the state of Sonora, Mexico. Our goals are to show which mechanisms (i.e., aeolian, marine) exert more influence on the composition of the Altar Desert dune sands. This study also shows the usefulness of REE spatial distribution to determine the relative mobility of the sand. Some sand samples from the dune systems in San Luis Río Colorado (SLRC), Golfo de Santa Clara (GSC), and Puerto Peñasco (PP) displayed dissimilar REE concentrations with respect to the rest of the sand samples from the same sites. These differences can be related to short aeolian transport distance in the sands with high REE concentrations and long aeolian transport distance in the sands with low REE concentrations. Besides, high REE concentration in the sands might be due to their closeness to the Colorado River Delta sediments and to recycled sands derived from granitic rocks. In contrast, all the sand samples from the El Pinacate (EP) site have similar REE concentration values, suggesting that the El Pinacate dune sands are influenced by more selective aeolian processes and less diverse heavy mineral content. The Altar Desert dune sands are derived from granitic sources eroded by the Colorado River. Our results also indicate that the Altar Desert dune sands are low in heavy mineral content (with the exception of Fe and Ti bearing minerals) and enriched in carbonates with phosphates (especially at the PP site) yielding poor correlations between REE and major element concentrations. The REE geographical distribution values in the Altar Desert dune sands indicate that light and heavy REE concentration values are related to aeolian transport, maturity of the sands, their low weathering rates, proximity of the source rocks, and the biogenic debris input from beach sands into the dune.     

气相色谱-质谱联用法测定土壤中邻苯二甲酸酯类增塑剂

应用加速溶剂萃取,气相色谱-质谱联用法测定土壤中6种邻苯二甲酸酯类有机污染物。对邻苯二甲酸酯类污染物的提取溶剂进行了优化选择,确定二氯甲烷作为最佳提取溶剂。对色谱柱升温程序进行了优化,以使两个出峰时间较接近的目标物邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)能够达到基线分离。方法标准曲线的线性范围为0.50～20.0mg/L,线性相关系数均大于0.9970,方法检出限为67μg/kg,加标回收率为81.9%～111.4%。方法检出限较低,精密度好,简便快速,可满足大批量样品分析对质量和进度的要求。     

Dissolved trace elements in river water: spatial distribution and the influencing factor, a study for the Pearl River Delta Economic Zone, China

Twenty-nine water samples were collected from different river channels of the Pearl River Delta Economic Zone, China. An inductively coupled plasma-mass spectromonitor (ICP-MS) was used to measure concentrations of the trace elements in these samples. The results suggest that the average concentrations of rare earth elements in river water show an increasing trend from the West River, the North River, the rivers of the Pearl River Delta, and the Shenzhen River to the East River. Relatively high concentrations of heavy metals appear in the East River, the rivers of the Pearl River Delta and the Shenzhen River, while the West River and the North River have relatively low heavy metal concentrations. Trace element concentrations in samples collected near urban or industrial areas are much higher than those of samples collected from distant areas, away from urban and industrial areas. After natural conditions, human activities have significant influence on the trace element concentrations in river water. This trace element concentration’s spatial distribution in the river water from the Pearl River Delta Economic Zone is actually an integrated effect of natural conditions and human activity.     

北京密云房山地区土壤中多环芳烃的组成与分布特征

选择北京城近郊房山与密云地区的土壤进行了多环芳烃的定量分析，同时探讨了多环芳烃在土壤中的分布特征与来源。研究结果显示：密云、房山两地土壤中多环芳烃的含量值具有明显差异，提示了两地工业活动影响强度的不同；各采样区土壤中多环芳烃总量的平均值在45．98～388．23ng／g变化，根据多环芳烃的特征参数可以推测研究区土壤中的多环芳烃主要来自于化石燃料的不完全燃烧。     

Empirical estimation of pollution load and contamination levels of phthalate esters in agricultural soils from plastic film mulching in China

Pollution load and contamination levels of phthalate esters (PAEs) in agricultural soils throughout China were studied in this work. The usage amount and residual rates of plastic film were the main factors explaining the variation among regions and leading to higher pollution load and contamination levels in agricultural big provinces. However, higher pollution loads and contamination levels frequently occurred under non-recycling than recycling scenarios during calculation. Extremely high loads (more than 10 kg/ha/year) of PAEs were estimated in five areas including Beijing city, Tibet, Liaoning Province, Jilin Province and Fujian Province and the high contamination levels in agricultural soil were presented in these places with more than 4.0 mg/kg under non-recycling scenarios. The predicted concentrations of PAEs in soils exceed the target value for soils from Netherlands (ΣPAEs = 0.1 mg/kg), indicating very high contamination of most Chinese agricultural soils. Significant differences in estimation results after plastic film utilization suggest that decreasing plastic film residue after application is an effective measure to control PAE pollution in soils. However, the comparison between contamination levels of PAEs estimated by the model and the previous detections of PAEs pollution levels in agricultural soils showed that there were presented wide range of PAE sources indicated to agricultural soils.     

Identifying water-quality trends in the Trinity River,Texas, USA, 1969–1992, using sediment cores from Lake Livingston

 Chemical analyses were done on cores of bottom sediment from three locations in Lake Livingston, a reservoir on the Trinity River in east Texas to identify trends in water quality in the Trinity River using the chemical record preserved in bottom sediments trapped by the reservoir. Sediment cores spanned the period from 1969, when the reservoir was impounded, to 1992, when the cores were collected. Chemical concentrations in reservoir sediment samples were compared to concentrations for 14 streambed sediment samples from the Trinity River Basin and to reported concentrations for soils in the eastern United States and shale. These comparisons indicate that sediments deposited in Lake Livingston are representative of the environmental setting of Lake Livingston within the Trinity River Basin. Vertical changes in concentrations within sediment cores indicate temporal trends of decreasing concentrations of lead, sodium, barium, and total DDT (DDT plus its metabolites DDD and DDE) in the Trinity River. Possible increasing temporal trends are indicated for chlordane and dieldrin. Each sediment-derived trend is related to trends in water quality in the Trinity River or known changes in environmental factors in its drainage basin or both. Received: 6 October 1995 · Accepted: 13 October 1995     

Biodegradation of phthalic acid esters in sewage sludge by composting with pig manure and rice straw

To comparatively study the biodegradation of phthalic acid esters (PAEs) in sewage sludge by composting with pig manure or with rice straw, four composting modes were designed: Mode 1 (sewage sludge + pig manure + intermittent aeration), Mode 2 (sewage sludge + pig manure + continuous aeration), Mode 3 (sewage sludge + rice straw + intermittent aeration) and Mode 4 (sewage sludge + rice straw + continuous aeration). Physicochemical parameters of composts were measured according to standard methods and PAEs were analyzed by gas chromatography coupled with mass spectrometry (GC/MS). The biodegradation of each PAE was also discussed. The results showed that Mode 1 was the best mode to biodegrade PAEs, which might be related to the wide class of indigenous microbial communities in pig manure and high efficiency of intermittent ventilation for providing oxygen. During the biodegradation process, di(2-ethylhexyl) phthalate was the most abundant and decisive for the removal of total PAEs. It showed a first-order kinetic degradation model. In conclusion, composting with pig manure could be suggested as an effective detoxification process for the removal of PAEs from sewage sludge, providing a safe end product.     

珠江三角洲经济区河水中微量元素的空间分布

在珠江三角洲经济区采集了29个河水样品,利用高分辨率仪器ICP MS测量了河水中微量元素的含量。结果表明,河水中稀土元素的平均含量按西江、北江、珠三角河、深圳河、东江的顺序呈增加趋势;珠三角河及深圳河具有较高重金属含量,西江和北江中重金属含量相对较低,东江居中。经分析发现,珠江三角洲经济区河水中微量元素的空间分布特征是自然条件和人类活动共同作用的结果;自然环境对稀土元素的空间分布起主要作用;人类活动是影响重金属分布特征不可忽视的重要因素。     

Gene abundances of AOA,AOB, and anammox controlled by groundwater chemistry of the Pearl River Delta,China

Ammonia-oxidizing archaea (AOA), ammonia-oxidizing bacteria (AOB), and anaerobic ammoniaoxidation (anammox) bacteria are very important contributors to nitrogen cycling in natural environments. Functional gene abundances of these microbes were believed to be well relevant to N-cycling in groundwater systems, especially in the Pearl River Delta (PRD) groundwater with unique high intrinsic ammonia concentrations. In this research, 20 sediment samples from two in the PRD were collected for porewater chemistry analysis and quantification of N-cycling related genes, including archaeal and bacterial amoA gene and anammox 16S ribosomal Ribonucleic Acid (rRNA) gene. Quantitative Polymerase Chain Reaction (qPCR) results showed that gene abundances of AOA, AOB, and anammox bacteria ranged from 3.13×10⁵ to 3.21×10⁷, 1.83×10⁴ to 2.74×10⁶, and 9.27×10⁴ to 8.96×10⁶ copies/g in the sediment of the groundwater system, respectively. Anammox bacteria and AOA dominated in aquitards and aquifers, respectively, meanwhile, the aquitard-aquifer interfaces were demonstrated as ammonium-oxidizing hotspots in the aspect of gene numbers. Gene abundances of nitrifiers were analyzed with geochemistry profiles. Correlations between gene numbers and environmental variables indicated that the gene abundances were impacted by hydrogeological conditions, and microbial-derived ammonium loss was dominated by AOA in the northwest PRD and by anammox bacteria in the southeast PRD.© 2021 China Geology Editorial Office.     

Activated sludge acclimation for toluene and DEHP degradation in a two-phase partitioning bioreactor

The effect of activated sludge acclimation on the biodegradation of toluene in the presence of a biodegradable non-aqueous phase liquid, di (2-ethylhexyl) phthalate (DEHP), in a two-phase partitioning bioreactor was characterized. The influence of the presence of DEHP, at a ratio of 0.1 % (volume ratio), and of the acclimation of activated sludge (AS) on the biodegradation of hydrophobic VOC was studied. AS was acclimated to both toluene and DEHP simultaneously. Using acclimated cells, 73 and 96 % improvement of the mean biodegradation rates was recorded for toluene and the organic solvent (DEHP), respectively, if compared to the values recorded in the absence of acclimation, during tests performed in Erlenmeyer flasks. Degradation rates were further improved by the use of acclimated AS in a reactor with a large head space; degradation yields for toluene and DEHP were above 99 and 89 %, respectively.     

Spatial variations and ecological risk assessment of heavy metals in surface sediments on the upper reaches of Hun River, Northeast China

The distribution, accumulation, and ecological risk of heavy metals (Cu, Cd, Pb, Zn, Ni, Cr, and As) in the surface sediment were investigated in the upper reaches of Hunhe River, Northeast China. Sediment samples from 51 points throughout the upper reaches of Hunhe River were collected and measured for heavy metal concentrations, TN content, and TP content. Results showed that heavy metal concentrations at the vicinity of mines and towns were higher than those at other locations. According to sediment quality guidelines (SQGs), Cd and Zn were enriched in the sediments. The correlation analysis and principal component analysis (PCA) were conducted to assess the heavy metal sources. Close correlations between metal distribution and TP indicated that the sediments may be affected by application of phosphate fertilizer. Elements, Cu, Cd, Pb, Zn, and As, were grouped together, reflecting they were released from the same sources. PCA suggested that their primary sources were anthropogenic, namely mining and extensive use of fertilizers. Therefore, heavy metal pollution due to mining and agricultural intensification in the upper Hunhe River basin should be taken into account during the formation of regional management strategies for the water environment.     

高温地热流体来源氟在环境中的分布特征——以西藏羊八井热田为例

西藏羊八井地热电厂产生的高氟废水直接排入了流经羊八井热田的藏布曲（河）。利用离子色谱仪（IC）测定了藏布曲水样的氟浓度;通过浸提实验提取了藏布曲河床沉积物中的总氟和各种存在形态的氟,并确定了其含量。藏布曲河水的氟浓度明显受到地热废水排放的影响,河床沉积物中水溶态氟和可交换态氟的分布也与地热电厂排污口的位置有明显的对应关系。然而,河床沉积物中的铁锰结合态氟、有机束缚态氟、残余态氟和总氟的分布与地热废水排放无显著联系,表明地热废水来源氟在进入藏布曲后主要向河床沉积物中的水溶态氟和可交换态氟转化。藏布曲河床沉积物是地热废水来源氟的一个汇。     

Historical pollution variability from abandoned mine sites,Greater Blue Mountains World Heritage Area,New South Wales,Australia

Core and surface sediments from the Tonalli River, a tributary of the artificial lake, Lake Burragorang, in the Blue Mountains National Park, New South Wales, Australia, were studied to evaluate the spatio-temporal distribution of pollutants from the Yerranderie silver-lead-zinc mine site, abandoned in the late 1920s. A sediment core was collected in the mouth of the Tonalli River, at its junction with Lake Burragorang, and surface sediment samples were collected in the Tonalli River and its tributaries. The concentrations of Pb, As, Zn, Cu, Cd, Hg and Ag in the sediments were determined by ICP-MS and ICP-AES techniques. Temporal variability of metal concentrations was established through ²¹⁰Pb dating of the core sediments and compared with published historical records, rainfall records and bushfire data. Metal concentrations in core sediments showed an overall increase around the year 1950 as well as increases coincident with heavy rainfall. Spatially, metal concentrations were up to 400 times the guideline limit around mine sites but decreased rapidly with distance downstream of the mines.     

Distribution and migration of pesticide residues in mosquito control impoundments St. Lucie County, Florida, USA

This project was designed to: (1) document the distribution and migration of organochlorine pesticide residues within marsh substrates of 18 St. Lucie County mosquito control impoundments located along the Indian River Lagoon estuary, and (2) evaluate the impact of water management techniques on residue mobility. Our results indicate that detectible concentrations of organochlorine compounds, applied between the late 1940s and early 1950s, are present in 16 of the 18 St. Lucie County mosquito control impoundments. These compounds are primarily restricted to the surficial, organic-rich wetland sediment, which, based upon geotechnical analysis, was exposed to the atmosphere at a time when the impoundments were subjected to pesticide treatment. Contaminated sediments are present below the surficial, organic-rich layer, suggesting that some vertical migration of pesticides has occurred. It is unlikely that leaching associated with the downward percolation of impounded water was responsible for this migration as pesticide residues were never detected within thein situ pore waters. An alternative explanation is that biological processes (e.g., rooting, burrowing) facilitated the downward flux of organochlorine compounds into sediment horizons not subjected to direct treatment. Eighty-eight surface water samples obtained from two impoundments subjected to contrasting water management techniques were analyzed for pesticide content. None of the surficial water samples collected in association with these impoundments contained detectible concentrations of organochlorine compounds. These samples were unfiltered and contained as much as 25 mg/1 of particulate organic matter. This suggests that the currently preferred management technique (RIM), which is designed to maintain water quality, limit mosquito production, and provide for ecological continuity, does not hydraulically mobilize pesticide residues into the Indian River Lagoon estuary.