应急处理苯胺污染水源水的粉末活性炭吸附工艺的研究

以浑河水为原水,模拟突发苯胺污染,通过投加粉末活性炭(PAC)进行应急处理的试验研究.试验结果表明:PAC对苯胺的吸附在30 min内能达到80%～90%的吸附容量;PAC对苯胺的吸附等温线符合弗兰德里希(Freundlich)吸附模式,在苯胺的平衡质量浓度为0.030 mg/L时,PAC对其吸附容量约为5 mg/g;比表面积较大的木屑炭对苯胺的吸附效果比煤质炭好,但粒度以300目左右为宜;炭浆浓度越小对苯胺的吸附效果越好;溶液pH以不小于5为最好;絮凝剂最佳的投加顺序是先投加炭浆然后投加絮凝荆;对突发的浑河水苯胺污染,在取水口处投加PAC是十分有效的应急处理措施.     

Heavy metals in bark of <Emphasis Type="Italic">Pinus massoniana</Emphasis> (Lamb.) as an indicator of atmospheric deposition near a smeltery at Qujiang,China

Goal, Scope and Background Rapid urbanization and the expansion of industrial activities in the past several decades have led to large increases in emissions of pollutants in the Pearl River Delta of south China. Recent reports have suggested that industrial emission is a major factor contributing to the damages in current natural ecosystem in the Delta area. Tree barks have been used successfully to monitor the levels of atmospheric metal deposition in many areas, but rarely in China. This study aimed at determining whether atmospheric heavy metal deposition from a Pb-Zn smeltery at Qujiang, Guangdong province, could be accurately reflected both in the inner bark and the outer bark of Masson pine (Pinus massoniana L.). The impact of the emission from smeltery on the soils beneath the trees and the relationships of the concentrations between the soils and the barks were also analyzed. Methods Barks around the bole of Pinus massoniana from a pine forest near a Pb-Zn smeltery at Qujiang and a reference forest at Dinghushan natural reserve were sampled with a stainless knife at an average height of 1.5 m above the ground. Mosses and lichens on the surface barks were cleaned prior to sampling. The samples were carefully divided into the inner bark (living part) and the outer bark (dead part) in the laboratory, and dried and ground, respectively. After being dry-ashed, the powder of the barks was dissolved in HNO₃. The solutions were analyzed for iron (Fe), manganese (Mn), copper (Cu), zinc (Zn), chromium (Cr), nickel (Ni) and cobalt (Co) by inductively coupled plasmas emission spectrometry (ICP, PS-1000AT, USA) and Cadmium (Cd) and lead (Pb) by graphite furnace atomic absorption spectrometry (GFAAS, ZEENIT 60, Germany). Surface soils (0–10 cm) beneath the sample trees were also collected and analyzed for the selected metals. Results and Discussion Concentrations of the selected metals in soils at Qujiang were far above their environmental background values in the area, except for Fe and Mn, whilst at Dinghushan, they were far below their background values, except for Cd and Co. Levels of the metals, in particular Pb and Zn, in the soils beneath the sample trees at Qujiang were higher than those at Dinghushan with statistical significance. The result suggested that the pine forest soils at Qujiang had a great input of heavy metals from wet and dry atmospheric deposition, with the Pb-Zn smeltery most probably being the source. Levels of Cu, Fe, Mn, Zn, Ni and Pb at Qujiang, both in the inner and the outer bark, were statistically higher than those at Dinghushan. Higher concentrations of Pb, Fe, Zn and Cu may come from the stem-flow of elements leached from the canopy, soil splash on the 1.5 m height and sorption of metals in the mosses and lichens growing on the bark, which were direct or indirect results from the atmospheric deposition. Levels of heavy metals in the outer barks were associated well with the metal concentrations in the soil, reflecting the close relationships between the metal atmospheric deposition and their accumulation in the outer bark of Masson pine. The significant (p<0.01) correlations of Fe-Cu, Fe-Cr, Fe-Pb, Fe-Ni, Pb-Ni, and Pb-Zn in the outer barks at Qujiang again suggested a common source for the metals. The correlation only occurred between Pb and Ni, Cd and Co in the outer barks at Dinghushan, which suggested that those metals must possibly have other uncommon sources. Conclusions Atmospheric deposition of the selected metals was great at Qujiang, based on the levels in the bark of Pinus massoniana and on the concentrations in the soils beneath the trees compared with that at Dinghushan. Bark of Pinus massoniana, especially the outer bark, was an indicator of metal loading at least at the time of sampling. Recommendations and Perspectives The results from this study and the techniques employed constituted a new contribution to the development of biogeochemical methods for environmental monitoring particularly in areas with high frequency of pollution in China. The method would be of value for follow up studies aimed at the assessment of industrial pollution in other areas similar with the Pearl River Delta.     

A decision framework for possible remediation of contaminated sediments in the River Kymijoki, Finland

Background, aim, and scope  The paper describes the spatial contamination of the River Kymijoki, South-Eastern Finland, and the coastal region of the Gulf of Finland with PCDD/Fs and mercury. The findings of ecotoxicologial and human health studies are also reported, including environmental and human risk assessments. Sediments from the River Kymijoki, draining into the Gulf of Finland, have been heavily polluted by the pulp and paper industry and by chemical industries. A wood preservative, known as Ky-5, was manufactured in the upper reaches of the river between 1940 and 1984 causing severe pollution of river sediments with polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). Moreover, the sediments have been polluted with mercury (Hg) from chlor-alkali production and the use of Hg as a slimicide in pulp and paper manufacturing. Materials and methods  An extensive sediment survey was conducted as well as sediment transport modeling, toxicity screening of sediment invertebrates, and a survey of contaminant bioaccumulation in invertebrates and fish. Studies on human exposure to PCDD/Fs and the possible effects on hypermineralization of teeth as well as an epidemiological study to reveal increased cancer risk were also conducted. An assessment of the ecological and human health risks with a null hypothesis (no remediation) was undertaken. Results  The sediment survey revealed severe contamination of river and coastal sediments with PCDD/Fs and Hg. The total volume of contaminated sediments was estimated to reach 5 × 10⁶ m³ and hot spots with extremely high concentrations (max 292,000 ng g⁻¹ or 1,060 ng I-TEQ g⁻¹ d.w.) were located immediately downstream from the pollution source (approximately 90,000 m³). Sediment contamination was accompanied by changes in benthic assemblages, but direct effects were masked by many factors. The fish showed only slightly elevated PCDD/F levels in muscle, but orders of magnitude higher in the liver compared with reference freshwater sites and the Baltic Sea. The concentrations in human fat did not reveal high human exposure in the Kymijoki area in general and was lower than in sea fishermen. The relative risk for total cancer among farmers was marginally higher (RR = 1.13) among those living close to the river, compared with farmers living further away, and the possibility of increased cancer risk cannot be ruled out. A conservative risk assessment revealed that the present probability of exceeding the WHO upper exposure limit of 4 pg WHO-TEQ kg⁻¹ d⁻¹ for PCDD/Fs and DL-PCBs was 6%. The probability of exceeding the WHO limit value of 0.23 μg kg⁻¹ d⁻¹ for methyl mercury was estimated to be notably higher at 62%. Based on these studies and the estimated risks connected with different remediation techniques a general remediation plan with cost benefit analysis was generated for several sub-regions in the river. Dredging, on-site treatment, and a close disposal of the most contaminated sediments (90,000 m³) was suggested as the first phase of the remediation. The decision regarding the start of remediation will be made during autumn 2008. Conclusions  The sediments in the River Kymijoki are heavily polluted with PCDD/Fs and mercury from earlier chlorophenol, chlor-alkali, and pulp and paper manufacturing. A continuous transport of contaminants is taking place to the Gulf of Finland in the Baltic Sea. The highly increased PCDD/F and Hg levels in river sediments pose an ecotoxicological risk to benthic fauna, to fish-eating predators and probably to human health. The risks posed by mercury exceed those from PCDD/Fs and need to be evaluated for (former) chlor-alkali sites and other mercury releasing industries as one basis for remediation decision making. Recommendations and perspectives  The studies form the basis of a risk management strategy and a plan for possible remediation of contaminated sediments currently under consideration in the Southeast Finland Regional Environment Centre. It is recommended that a detailed restoration plan for the most seriously contaminated areas should be undertaken. Based on current knowledge, the restoration of the whole river is not feasible, considering the current risk caused by the contaminated sediment in the river and the costs of an extensive restoration project. The experiences gained in the present case should be utilized in the evaluation of PCDD/F- and mercury-contaminated sites in other countries. The case demonstrates that the historic reservoirs are of contemporary relevance and should be addressed, e.g., in the national implementation plans of the Stockholm Convention. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

EU-wide survey of polar organic persistent pollutants in European river waters

This study provides the first EU-wide reconnaissance of the occurrence of polar organic persistent pollutants in European river waters. More than 100 individual water samples from over 100 European rivers from 27 European Countries were analysed for 35 selected compounds, comprising pharmaceuticals, pesticides, PFOS, PFOA, benzotriazoles, hormones, and endocrine disrupters. Around 40 laboratories participated in this sampling exercise. The most frequently and at the highest concentration levels detected compounds were benzotriazole, caffeine, carbamazepine, tolyltriazole, and nonylphenoxy acetic acid (NPE₁C). Only about 10% of the river water samples analysed could be classified as “very clean” in terms of chemical pollution. The rivers responsible for the major aqueous emissions of PFOS and PFOA from the European Continent could be identified. For the target compounds chosen, we are proposing “indicative warning levels” in surface waters, which are (for most compounds) close to the 90th percentile of all water samples analysed.     

Reprint of: Concentrations, distribution, and bioaccumulation of synthetic musks in the Haihe River of China

Seven typical synthetic musks (SMs) in the samples from the surface water, sediment and fish of the Haihe River were measured. The SM concentrations in the sediment and surface water of the Haihe River were significantly lower than those in the Dagu Drainage River and Chentaizi Drainage River (p < 0.05). Along the flow direction, the SM concentrations in surface water and sediment tended to increase from the upstream to the downstream of Dagu Drainage River. The Bioaccumulation factors (BAFs) of galaxolide (HHCB) and tonalide (AHTN) were calculated at high levels in the muscles of crucian carp, common carp, and silver carp. Most of the biota-sediment accumulation factors (BSAFs) for HHCB and AHTN were higher than 1.7, suggesting magnification possibly exist in the musk bioaccumulations of the three fishes in the Haihe River. No significant differences in HHCB/AHTN ratios were observed among the water, fish, and sediment samples (p > 0.05). However, the HHCB/AHTN values in the Haihe River were much lower than those in the Dagu Drainage River and Chentaizi Drainage River (p < 0.05). Compared with several typical persistent organic pollutants (POPs), the musk concentrations were higher or comparable in the Haihe River.     

Occurrences of pharmaceutical and personal care products as micropollutants in rivers from Romania

The occurrence of pharmaceutical and personal care products (PPCPs) was investigated in the Somes River. The aim of this study was to obtain a first overview about the contamination of Somes River (Transylvania) with PPCPs. The samples were preconcentrated by Solid Phase Extraction (SPE) procedures and analysed by GC/MS. A number of 15 compounds including pharmaceutics, metabolites, intermediates and musk fragrances were detected in concentration ranging from 30 ng/l to 10 μg/l. The detected pharmaceuticals are included in following therapeutic groups: analgesics, antiepileptics, psychiatric, stimulants, anticoagulants, antineoplastic and disinfectants.     

"十一五"脱硫计划实施前后长三角地区的硫沉降变化

采用RAINS ASIA模型研究了"十一五"期间长三角地区实施脱硫措施前后硫沉降超临界负荷的变化.结果表明,在90%保证率下,长三角地区硫沉降的临界负荷(以S计,下同)总值为78.38万t/a;2005年该地区硫沉降的超临界负荷总值为27.98万t/a,有45.6%区域面积的硫沉降超过临界负荷;如果不实施脱硫措施,到2010年长三角地区硫沉降超临界负荷的情景将急剧恶化,硫沉降超临界负荷总值将增长18.4%,超临界负荷的区域面积将增加到48.7%;"十一五"脱硫计划如期实施后,2010年长三角地区硫沉降超临界负荷总值将在2005年的基础上下降27.4%,但仍有39.1%的区域面积超过临界负荷,须采取更严格的措施控制硫沉降量.     

海河干流、大沽排污河沉积物中有机氯农药的残留状况

调查了海河干流和大沽排污河沉积物中持久性有机氯杀虫剂(OCPs)的残留状况.在所选取的16个断面沉积物样品中均有大量HCHs、DDTs检出,表明海河和大沽排污河的DDT和HCH污染相当严重.海河沉积物中HCHs和DDTs总质量浓度分别为3.30～75.96、1.57～221.57 ng/g.大沽排污河沉积物中HCHs和DDTs的残留量分别为2.30～124.61、11.28～237.30ng/g.与国内外部分河流表层沉积物中HCHs、DDTs的含量相比,海河和大沽排污河沉积物中有机氯农药含量较高.最后根据两条河流沉积物中的OCPs的残留量,分析了其可能的污染源.     

Occurrence, sources, and inventory of hexabromocyclododecanes (HBCDs) in soils from Chongming Island, the Yangtze River Delta (YRD)

Hexabromocyclododecanes (HBCDs) is a concern due to their large usage combining with physico-chemical properties and toxicity to wildlife and human. However, very limited data were reported on HBCDs in soils, especially from rural area. In this study, 22 soil samples were collected from Chongming Island at estuary of the Yangtze River Delta, to investigate the level, diasteroisomer profile, potential sources, and mass inventory of HBCDs. The total concentrations ranged from not detected to 93.8 pg g⁻¹ dry weight (dw) with a mean of 23.3 pg g⁻¹ dw, which was at the low end of the global levels. The wide distribution of HBCDs in soils suggested that the local emissions of HBCD-containing materials and/or the inputs via atmospheric transport from other regions were two possible sources. Variation of HBCDs levels was observed in different types of soils. Woodland, tideland and road soils contained slightly higher HBCDs than those of farmland and grassland. Overall, γ-HBCD was the dominant diasteroisomer in soils, followed by α-HBCD and β-HBCD. Significant but weak correlations were only found between α-HBCD and β-HBCD versus TOC content in soils. Currently, the mass inventory of HBCDs in soils of Chongming Island was 5.3 kg. Based on these data, we gave perspective on human intake of HBCDs via soil ingestion by age. Local resident’s intakes ranged from 15.5 to 97.8 fg kg body weight⁻¹ d⁻¹, in which children are exposed more than adults.     

PCB accumulation and tissue distribution in cave salamander (Proteus anguinus anguinus, Amphibia, Urodela) in the polluted karstic hinterland of the Krupa River, Slovenia

For over two decades, a manufacturer of electrical capacitors disposed of its waste within the karstic hinterland of the Krupa River (Slovenia) resulting in the surroundings becomming heavily polluted with PCB. Albeit the extent of the contamination has been known since 1983 and the Krupa River has become one of the most PCB polluted river in Europe, the effects on the cave fauna of the region remain unknown. The most famous cave dweller of the Krupa hinterland is the endemic cave salamander Proteus anguinus anguinus. In this study we determine the levels of PCB in the tissues of the Proteus and in river sediments. The total concentration of PCB in individual tissue samples from specimens of the Krupa spring was between 165.59 μg g⁻¹ and 1560.20 μg g⁻¹ dry wt, which is at least 28-times higher than those from an unpolluted site. The kidneys contained the lowest concentration, while the highest concentration was in subcutaneous fat and tissues with high lipid contents like visceral fat and liver. Total PCB concentrations in sediment samples from the Krupa River were between 5.47 and 59.20 μg g⁻¹ dry wt showing that a high burden of PCB still remains in the region. The most abundant PCB congeners in all analyzed samples were di-ortho substituted (PCB #101, #118, #138 and #158), but higher proportion of mono-ortho PCB was present in sediments. The ability of Proteus to survive a high PCB loading in its environment and especially in its tissues is remarkable. Its partial elimination of low chlorinated and mono-ortho substituted congeners is also reported.