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.     

The occurrence of antihistamines in sewage waters and in recipient rivers

Background, aim and scope  Each year, large quantities of pharmaceuticals are consumed worldwide for the treatment and prevention of human and animal diseases. Although the drugs and the metabolites observed in the wastewaters and in the environment are present at concentrations several orders of magnitude lower than the concentrations required to exert their effects in humans or animals, their long-term impact on the environment is commonly not known. In this study, the occurrence of six antihistamines, which are used for the relief of allergic reactions such as hay fever, was determined in sewage treatment plants wastewaters and in recipient river waters. Materials and methods  The occurrence of the antihistamines cetirizine, acrivastine, fexofenadine, loratadine, desloratadine and ebastine in sewage treatment plants wastewaters and in recipient river waters was studied. The analytical procedure consisted of solid-phase extraction of the water samples followed by liquid chromatography separation and detection by a triple-quadrupole mass spectrometer in the multiple reaction mode. Results  Cetirizine, acrivastine and fexofenadine were detected in both influent and effluent wastewater samples at concentration levels ranging from about 80 to 220 ng/L, while loratadine, desloratadine and ebastine could not be detected in any samples. During sewage treatment, the concentration of the antihistamines dropped by an average of 16–36%. Furthermore, elevated concentrations of antihistamines were observed in samples collected during the season of most intensive plant pollen production, i.e. in May. In the river water samples, the relative pattern of occurrence of cetirizine, acrivastine and fexofenadine was similar to that in the wastewater samples; although the concentration of the compounds was substantially lower (4–11 ng/L). The highest concentrations of the studied drugs were observed near the discharging point of the sewage treatment plant. Discussion  The highest concentrations of antihistamines in STP wastewaters correlate with the outbreak of allergic reaction caused by high amounts of plant pollens in the air. The analysis results of the river water samples show that the antihistamines are carried far away from the effluent discharge points. They may account for a part of the mix of pharmaceuticals and of pharmaceutical metabolites that occur downstream of STPs. Conclusions  Antihistamines are poorly degraded/eliminated under the biological treatment processes applied in the wastewater treatment plants and, consequently, they are continuously being discharged along with other drugs to the aquatic environment. Recommendations and perspectives  As a huge quantity and variety of drugs and their metabolites are continuously discharged to rivers and the sea, the compounds should be considered as contaminants that may possess risks to the aquatic ecosystem. Further studies are urgently needed on the environmental fate of the antihistamines and other pharmaceuticals in the aquatic environment. These studies should be concerned with the stability of the compounds, their transformation reactions and the identity of the transformation products, the distribution of drugs and their uptake and effects in organisms. On the basis of these studies, the possible environmental hazards of pharmaceuticals may be assessed.     

人工浮床对汾江河水质净化的研究

对佛山市汾江河内布置浮床的水域的7个断面进行采样监测,分析了布置浮床侧与未布置浮床侧各水质指标的差异,以考察人工浮床对汾江河水质的净化效果。同时比较了圆币草、水罂粟、梭鱼草、狐尾草、美人蕉和鸢尾6种浮床植物的生物量和氮磷吸收量。结果表明,布置人工浮床一侧的水质TN、TP、COD和NH4＋-N含量均显著低于未布置浮床一侧的水质,表明人工浮床对水体水质的有净化效果。总面积约4 900 m2的浮床植物经过3个月的生长,从水体中共吸收了192.5 kg的氮和76.1 kg的磷。6种浮床植物中,狐尾草的净增生物量最高,达到64.2 kg/m2;圆币草次之,为62.2 kg/m2。狐尾草和圆币草对氮磷的吸收能力在6种植物中处于较高水平,每平方米狐尾草和圆币草从水体中分别吸收了51.61g氮、19.79 g磷和46.90 g氮、22.93 g磷。综合比较得出,狐尾草和圆币草在生物量和氮磷吸收量上均保持在较高水平,是较好的浮床植物。本研究为人工浮床在南方类似河流中的应用及植物选择提供了参考依据。     

Occurrence, source diagnosis, and biological effect assessment of DDT and its metabolites in various environmental compartments of the Pearl River Delta, South China: A review

This review summarizes and analyzes available data in the literature (mostly after 2000) on the occurrence of dichlorodiphenyltrichloroethane (DDT) and its main metabolites, dichlorodiphenyldichloroethane (DDD) and chlorodiphenyldichloroethylene (DDE), in the environment of the Pearl River Delta (PRD), South China. Generally, the concentration levels of the sum of DDT, DDD, and DDE, designated as DDTs thereafter, have not significantly declined since 1983. However, the composition of DDTs residues has changed with time. DDTs in soil, freshwater sediment and freshwater fish species were mainly residues from chronological use. There is evidence that new point sources, such as dicofol and anti-fouling paint, may have contributed DDTs to various environmental compartments. Risk assessment against existing criteria indicated that the levels of DDTs in water and some fish species may pose adverse effects to humans or wildlife, and those in sediment/soil may also cause negative impacts to the eco-environment of the PRD.     

Perfluorinated compounds in the Pearl River and Yangtze River of China

A total of 14 perfluorinated compounds (PFCs) were quantified in river water samples collected from tributaries of the Pearl River (Guangzhou Province, south China) and the Yangtze River (central China). Among the PFCs analyzed, perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were the two compounds with the highest concentrations. PFOS concentrations ranged from 0.90 to 99 ng/l and <0.01–14 ng/l in samples from the Pearl River and Yangtze River, respectively; whereas those for PFOA ranged from 0.85 to 13 ng/l and 2.0–260 ng/l. Lower concentrations were measured for perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), perfluorooctanesulfoamide (PFOSA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorononaoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUnDA). Concentrations of several perfluorocarboxylic acids, including perfluorododecanoic acid (PFDoDA), perfluorotetradecanoic acid (PFTeDA), perfluorohexadecanoic acid (PFHxDA) and perfluorooctadecanoic acid (PFOcDA) were lower than the limits of quantification in all the samples analyzed. The highest concentrations of most PFCs were observed in water samples from the Yangtze River near Shanghai, the major industrial and financial centre in China. In addition, sampling locations in the lower reaches of the Yangtze River with a reduced flow rate might serve as a final sink for contaminants from the upstream river runoffs. Generally, PFOS was the dominant PFC found in samples from the Pearl River, while PFOA was the predominant PFC in water from the Yangtze River. Specifically, a considerable amount of PFBS (22.9–26.1% of total PFC analyzed) was measured in water collected near Nanjing, which indicates the presence of potential sources of PFBS in this part of China. Completely different PFC composition profiles were observed for samples from the Pearl River and the Yangtze River. This indicates the presence of dissimilar sources in these two regions.     

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.     

"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.     

Structural and optical characterization of dissolved organic matter from the lower Athabasca River, Canada

Dissolved organic matter (DOM) is a ubiquitous constituent of natural waters and is comprised of a variety of chemically heterogeneous molecular structures and functional groups. DOM is often considered to be a major ligand for metals in most natural waters and its reactivity is thought to be strongly dependent on its chemical composition and structure. In this study, a combination of UV/visible, emission excitation matrix fluorescence (EEM) and ¹H NMR spectroscopies were used to characterize DOM from the Athabasca River (Alberta, Canada). The chemical characterization of river DOM showed that the most upstream samples located in agricultural areas were blue-shifted and less aromatic and contained more hydrogens connected with oxygen functional groups than those in the wetland dominated area in the Athabasca oil sand deposit region. The presence of paramagnetic ions (Fe and Al) was not found to significantly affect the structural composition of DOM as revealed by ¹H NMR. Such change in the quality of DOM may have a profound impact on metal binding in the Athabasca River watershed.     

有色金属冶炼区铊(Tl)的水环境分布特征与环境对策--以大冶冶炼厂地区的东岗河为例

以大冶冶炼厂地区的东岗河为例,分析有色金属冶炼区铊的水环境分布特征,结果表明：河水中的铊含量明显异常(严重污染区的平均含量为15．07ng／mL。远超过饮用水源水中铊的最高允许浓度0．1ng／mL)．且与水体pH值、Cu^2 、Pb^2 等含量显著相关;铊与Pb等亲铜元素呈类质同像。宏观上与方铅矿、闪锌矿、黄铁矿、黄铜矿等伴生．因此后者成为研究区铊的重要来源。最后,对铊所造成的环境危害效应．提出相应的解决对策,并提醒人们提高对铊污染的警惕性以及加深对铊的研究。     

周边土地利用类型对川西平原西河氮素的影响

以四川盆地西部典型农业小流域为研究区,于2015年3月~2016年2月持续监测河流氮素（NH₄⁺-N、NO₃^--N、TN）和pH,结合遥感解译、地理信息系统和相关性分析等技术,探讨了监测断面周边流域土地利用类型与河流氮素及pH值的关系.结果表明,研究区河流氮素浓度的季节变化均表现为冬季最高（2.063mg/L）、春秋次之（1.536mg/L;1.432mg/L）、夏季最低（1.085mg/L）,同时月均NO₃^--N浓度（0.891mg/L）显著高于NH₄⁺-N（0.425mg/L）（P<0.01）,且NO₃^--N受到典型土地利用类型的显著影响.随着缓冲区半径的增加,耕地、城乡建设用地和水域的面积与NO₃^--N和TN浓度相关性逐渐降低,且在250m缓冲区内,城乡建设用地面积与NO₃^--N浓度呈显著正相关（P<0.05）;交通运输用地面积与所有氮组分的相关性均增大,且在750m缓冲区内,交通运输用地面积与NO₃^--N和TN浓度呈极显著正相关（P<0.01）.城乡建设用地和交通运输用地可能是河流NO₃^--N的"源".