Acid mine drainage pollution in the Tinto and Odiel rivers (Iberian Pyrite Belt, SW Spain) and bioavailability of the transported metals to the Huelva Estuary

The Tinto and Odiel rivers are seriously affected by acid mine drainage (AMD) from the long-term mining activities in Iberian Pyrite Belt (IPB). As a consequence, the Huelva estuary is heavily contaminated by metals and metalloids. This study presents an estimation of the seasonal variation, and the dissolved contaminant load transported by both rivers from February 2002 to September 2004. Besides, toxicity and bioaccumulation tests with the sediments of the estuary have been conducted in order to measure the mobility of the toxic metals. Results show that the Tinto and Odiel rivers transport enormous quantities of dissolved metals to the estuary: 7900 t yr(-1) of Iron (Fe), 5800 t yr(-1) Aluminium (Al), 3500 t yr(-1) Zinc (Zn), 1700 t yr(-1) Copper (Cu), 1600 t yr(-1) Manganese (Mn) and minor quantities of other metals and metalloids. These values represent 37% of the global gross flux of dissolved Zn transported by rivers in to the ocean, and 15% of the global gross flux of dissolved Cu. These metals and metalloids usually sink in the estuarine sediments due to pH and salinity changes. The increase of salinity in the estuary favours the adsorption and trapping of metals. For this reason, the mobility and bioavailability of metals such as Zn, Cd and Cu is higher in sediments located in the area of fresh water influence that in sediments located in the marine influenced area of the estuary, showing a higher percentage of fractionation and bioaccumulation of these metals in the station influenced by the fresh water environment.     

污染河道的常量和微量元素特征及指示意义

河道常量元素和微量元素的分布既反映了不同的来源,又显示了污染水平。选择太湖周边具有不同污染源特征的漕桥河、梁溪河和大浦河,针对水体、悬浮物、沉积物3种不同介质,研究其化学元素含量及变化。微量元素特征及变化分析表明,3条河流整体上磷的含量较高,金属元素在城镇和工业区河段较高。元素主成分分析显示,接纳工业废水、生活污水和农田径流的河流,主成分组成差别明显。元素特征对比值结果表明,不同介质中元素对的变化并不一致,不同河道大体反映了工业废水、农田径流和生活污水的特点;分配系数〖WTBX〗KD〖WTBZ〗值的大小顺序为Fe>Al>Zn>Cr>Ni>K,多数元素的〖WTBX〗KD〖WTBZ〗值都是漕桥河最高,梁溪河最低,Zn的〖WTBX〗KD〖WTBZ〗值则是大浦河最高,漕桥河最低,反映了不同污染源的特征差别。指示元素的研究对于污染河道的治理是有意义的。     

鄱阳湖水土环境及其水生维管束植物重金属污染

位于鄱阳湖流域乐安河中下游的德兴铜矿,是我国著名的大型铜业基地,是鄱阳湖流域重金属污染的主要来源之一。2003年7月至8月对鄱阳湖部分流域的水质、沉积物、底泥及水生维管束植物等样品的重金属污染进行了研究调查,采用原子吸收分光光度法分别对样品中的Cu、Zn、Pb、Cd等重金属含量进行了测定,并对测定结果进行了评价。研究结果表明,鄱阳湖流域水体中的重金属含量均达到地表水评价标准中的Ⅰ类标准,底泥、土壤等已受到了一定程度的重金属污染。而水生植物对重金属元素都具有不同程度的富集能力,植物对重金属的富集作用与土壤背景值有一定的相关性,土壤中重金属的背景值越高,植物对重金属的富集量也相应增加。     

Radionuclides from past uranium mining in rivers of Portugal

During several decades and until a few years ago, uranium mines were exploited in the Centre of Portugal and wastewaters from uranium ore milling facilities were discharged into river basins. To investigate enhancement of radioactivity in freshwater ecosystems, radionuclides of uranium and thorium series were measured in water, sediments, suspended matter, and fish samples from the rivers Vouga, D?o, Távora and Mondego. The results show that these rivers carry sediments with relatively high naturally occurring radioactivity, and display relatively high concentrations of radon dissolved in water, which is typical of a uranium rich region. Riverbed sediments show enhanced concentrations of radionuclides in the mid-section of the Mondego River, a sign of past wastewater discharges from mining and milling works at Urgeiri?a confirmed by the enhanced values of (238)U/(232)Th radionuclide ratios in sediments. Radionuclide concentrations in water, suspended matter and freshwater fish from that section of Mondego are also enhanced in comparison with concentrations measured in other rivers. Based on current radionuclide concentrations in fish, regular consumption of freshwater species by local populations would add 0.032 mSv a(-1) of dose equivalent (1%) to the average background radiation dose. Therefore, it is concluded that current levels of enhanced radioactivity do not pose a significant radiological risk either to aquatic fauna or to freshwater fish consumers.     

The effect of floods on the transport of suspended sediments and contaminants: a case study from the estuary of the Dese River (Venice Lagoon, Italy)

A flood event was investigated in a measurement section of the estuary of the Dese River, the major tributary of the Venice Lagoon (mean annual discharge=7.5 m3/s), to observe the variations induced by the flow on the physico-chemistry of the water column and the transport of particles and pollutants. The flood was generated by a typical summer storm, which had a return period of 2 years. The study was based on the continuous recording of the discharge and the measurement of both current speed and physico-chemical variables along the vertical profile. Water samples were also collected for the analysis of total and dissolved heavy metals (As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Zn), and nutrients (TKN, N-NO3-, N-NO2-, N-NH3, total phosphorous, P-PO43-). The suspended particle matter (SPM) concentration increased in the water column during the flood, and the discharge versus SPM relationship showed a counterclockwise hysteresis. The occurrence of hysteresis was related to the delayed response of the load, deriving from the runoff on the basin soils with respect to materials mobilized from the streambed in the initial phases of the flood. The transport of most of the analysed heavy metals was driven by the SPM. The increase in concentration of this parameter significantly affected the amount of Fe, Cu, Pb, Cr, Ni, and partially Zn transported by the stream. Among nutrients, N-NO3- concentration also increased significantly during the flood, due to the runoff on agricultural surfaces. The study allowed describing the mechanisms of load generation with high flow magnitudes, highlighting the importance of floods in the transport of materials and pollutants from the drainage basin to the Venice Lagoon.     

河口泥沙再悬浮对悬沙中重金属元素的影响

基于1997年3月9日和7月27日长江口南槽定点连续观测资料。分析了河口泥沙再悬浮对重金属元素的影响。研究结果表明，在长江口南槽，近底悬沙浓度和悬沙中重金属含量均随时间变化而变化，且两者具有良好的对应关系；因子分析结果显示对所有金属元素都占绝对优势的F1因子为泥沙再悬浮，泥沙再悬浮现象对本次观测中近底泥沙中重金属含量变化起主导作用。泥沙再悬浮一方面会导致悬沙和床沙的混合。另一方面有可能导致重金属从泥沙中向水体中再释放，在长江口南槽，枯季近底悬沙中重金属含量的变化主要缘于悬沙、床沙的混合；而洪季除悬沙和床沙混合之外，还存在泥沙再悬浮过程泥沙中重金属的释放，这可能与洪季高水温、低溶氧等环境因素以及强烈的水动力条件有关。     

近期长江口南支河道洪季含沙量时间变化及床沙再悬浮研究

基于2011年洪季在南支河道从小潮至大潮连续8天现场定点观测所获得水沙观测数据(包括潮流、悬沙浓度、悬沙粒度和表层沉积物样品),通过对悬沙浓度、悬沙粒度和沉积物在不同时刻的组成分析,以及流速、悬沙和底床切应力的相互影响分析,对长江河口南支河道悬沙随时间变化特性和河床沙再悬浮作用进行了研究。结果表明:观测期间南支主槽下段落潮水动力强于涨潮;落潮悬沙浓度高于涨潮,并由小潮至大潮逐渐增加;落潮悬沙粒径粗于涨潮,并随小潮至大潮不断粗化;河床沉积物颗粒较粗,细砂类组成达到90%以上;流速、悬沙及底床切应力之间存在显著相关性;河床泥沙再悬浮强度较强,其量值有限。而近期研究区域悬沙浓度和水沙关系发生变化,与流域来沙出现锐减有关。     

Prospects of using mosses (<Emphasis Type="Italic">Fontinalis antipyretica</Emphasis> Hedw. and <Emphasis Type="Italic">Pylaisia polyantha</Emphasis> (Hedw.) Bruch et al.) as indicators of environmental contamination with heavy metals

The contents of Al, Ti, Fe, Cr, Cu, Zn, As, Se, Cd, Pb, and rare earth elements (REEs) were determined in mosses (the hydrophyte Fontinalis antipyretica and the epiphyte Pylaisia polyantha) by the inductively coupled plasma-mass spectrometry (ICP-MS) method. These plants were used for estimating the spatial distribution of heavy metals (HMs) in the basins of small and medium rivers of Vologda and Kostroma oblasts (Russia). It was shown that water mosses are good indicators of REEs and epiphytic mosses, of the pollutant metals Cu, Zn, Se, and Pb. The epiphytic and hydrophytic mosses did not differ in the macroelement (Al, Ti, and Fe) content.     

Nutrient export by rivers to the coastal waters of China: management strategies and future trends

We analyzed past and future trends in river export of dissolved nitrogen (N) and phosphorus (P) to the coastal waters of China, for a selection of rivers, as calculated by the Global NEWS models (Nutrient Export from WaterSheds). Over the period 1970–2000, river export of dissolved nutrients increased considerably, especially of dissolved inorganic N and P. Anthropogenic sources of N and P in rivers have become increasingly important, in particular N and P losses from agriculture. We tested the sensitivity of calculated nutrient export by rivers to changes in selected controlling factors. The calculated export of dissolved N and P is sensitive to changes in hydrology, synthetic fertilizer use and manure excretion in river basins. Changes in sewage inputs have large effects on dissolved inorganic P export. We analyzed future trends up to 2050 for several scenarios to illustrate the combined effects of selected management options. In the Base Scenario, the N and P export by the selected rivers increases considerably between 2000 and 2030. The increase continues from 2030 to 2050 except for DIP. Strategies to reduce N and P export by rivers include changes in agriculture, sewage and energy use. Changes in agriculture have the largest impact on future dissolved N and P river export to the coastal waters of China. The effectiveness of reduction strategies differs between nutrient forms and basins.     

黄浦江表层沉积物中重金属污染的潜在生态风险评价

采用潜在生态风险指数法对黄浦江表层沉积物中重金属污染的潜在生态风险进行了评价。评价结果表明,黄浦江表层沉积物中重金属的潜在生态风险水平较低,其中杨浦大桥和南市水厂断面达到中等生态风险,其它断面均为轻微生态风险;重金属的潜在生态风险依次为Cd>Hg>Cu>As>Pb>Cr>Zn,除Cd达到中等生态风险外,其余元素均为轻微生态风险。沉积物中重金属的污染水平从上游到下游呈上升趋势,工业排放是水环境中重金属的主要来源,苏州河对黄浦江下游重金属存在一定的输入贡献。相关性分析表明,黄浦江表层沉积物中大多数重金属元素呈现相近的来源特征,有机质是影响沉积物中重金属分布的重要因素。     

Distribution of U-Th nuclides in the riverine and coastal environments of the tropical southwest coast of India

A reconnaissance study has been made on the distribution of 238U, 234U, 232Th and 230Th in soils, water, suspended particulate matter (SPM) and bottom sediments in the Kali river basin around Kaiga, its estuarine region and the adjacent Arabian Sea to obtain the baseline data of U-Th series nuclides in view of the commissioning of nuclear power reactors at Kaiga, near Karwar, on the southwest coast of India. Drainage basin soils developed over greywackes (the dominant litho-unit upstream) are lower in 238U/Al and 232Th/Al ratios by factors of 3-5 in comparison with those developed over tonalitic gneisses (the dominant litho-unit downstream). The dominance of the former type of soils is reflected in the composition of river-bottom sediments derived from the upstream drainage basin during the monsoon. The 232Th in bottom sediments tends to increase towards the estuarine and coastal areas, presumably due to deposition of heavy minerals and onshore transport of coastal sediments into the estuary. The dissolved U in the Kali river is low (0.001-0.02 microg/l) when compared to the major Indian rivers as the Kali river flows through U-poor greywackes. Thus, the input of dissolved U to the Kali estuary is dominated by sea water. Although there is some evidence for the removal of dissolved U at low salinity during estuarine mixing, its behaviour is conservative in the lower estuary (at higher salinities). The removal rate of dissolved U from the Kali river basin is similar to that reported from other tropical river basins. The U flux from all the west-flowing rivers of Peninsular India is estimated at 26.3 x 10(6) g/yr to the Arabian Sea which is about 2% of the flux from the Himalayan rivers to the Bay of Bengal.     

Anthropogenic impacts on suspended sediment load in the Upper Yangtze river

Climate change and human disturbance drive catchment erosion and increase riverine sediment load sensitively in small and medium-sized watersheds. This is not always true in large basins, where aggregation and buffering effects have dampen the ability to determine the driving forces of sedimentation. Even though there are significant responses to sedimentation in large river basins, it is difficult to get a precise quantitative assessment of specific drivers. This paper develops a methodology to identify driving forces that change suspended sediment load in the Upper Yangtze river. Annual runoff and sediment load data from 1954 to 2005 at the Yichang gauging station in the Upper Yangtze basin, daily precipitation data from 60 meteorological stations, and survey data on reservoir sediment were collected for the study. Sediment load/rainfall erosivity (S/R), is a new proxy indicator introduced to reflect human activities. Since the mid-1980s, S/R in the Upper Yangtze has dramatically declined from 0.21 to 0.03 (×10¹⁰ t ha h MJ⁻¹ mm⁻¹), indicating that human activity has played a key role in the decline of the suspended sediment load. Before the mid-1980s, a higher average S/R is attributed to large-scale deforestation and land reclamation. A significant sediment decrease occurred from 1959 to 1961 during an extreme drought condition, and an increase in sedimentation in 1998 coincided with an extreme flood event, which was well recorded in the S/R curve. This indicates that the S/R proxy is able to distinguish anthropogenic from climate impacts on suspended sediment load, but is not necessarily indicatory in extreme climate events. In addition, typical drivers of riverine sediment load variation including soil conservation projects, reservoirs construction, and land use/cover change are discussed.     

Contaminant mobility in diked containment areas

Nine dredged material land containment areas, located at upland, lowland, and island sites, were monitored during hydraulic dredging operations in fresh and brackish-water riverine, lake, and estuarine environments. Influent/effluent sampling at the diked disposal areas showed that, with proper retention of suspended solids, most chemical constituents could be removed to near background water levels. Most heavy metals, oil and grease, chlorinated pesticides, and PCBs were almost totally associated with solids in both the influent and effluent samples. The parameters that appear to have the greatest potential impact as a result of land disposal of dredged material are ammonia, soluble manganese, total mercury, and dissolved oxygen; soluble iron, zinc, and copper may occasionally exceed criteria or background levels.v However, none of these should present serious problems after dillution of the effluent discharge in the receiving waters. Actively growing vegetation in disposal areas appeared to be efficient in removing ammonium nitrogen to low levels and also for filtering out suspended solids. Dissolved oxygen in effluents ranged from 0.6 to 12.5 ppm. Geochemical phase partitioning of influent and effluent solids indicated that carbonate solids of several heavy metals tended to form during dredged slurry containment, promoted by high alkalinity and increased pH in site waters. Metal adsorption onto effluent suspended particles (exchangeable phase) increased slightly, along with a significant increase in cation exchange capacity.     

长江口洋山海域表层沉积物重金属的富积及其潜在生态风险评价

根据长江口洋山海域表层沉积物监测资料，利用变异系数法和富积系数法，对表层沉积物中重金属的空间波动程度及富积程度进行了分析，并采用Hakanson潜在生态危害指数法对其潜在生态危害程度进行了评价。结果表明：在表层沉积物所监测的重金属中，Pb元素的空间波动程度最高，其它重金属元素的空间波动程度较低，各重金属空间波动程度的顺序依次为Pb＞Cd＞Hg＞Cu＞Cr＞As＞Zn；沉积物中Cu元素的富积程度最高，Pb元素次之，其它重金属元素的富积程度较低，各重金属富积程度的顺序依次为Cu＞Pb＞Zn＞As＞Cr＞Cd＞Hg。潜在生态危害评价结果显示：洋山海域表层沉积物中的重金属对海洋生态系统的潜在生态危害较轻微，均属于轻微潜在生态危害程度，其轻微潜在生态危害程度顺序为Cu＞As＞Hg＞Pb＞Cd＞Cr＞Zn。     

Characterisation of heavy metal discharge into the Ria of Huelva

The Ria of Huelva estuary, in SW Spain, is known to be one of the most heavy metal contaminated estuaries in the world. River contribution to the estuary of dissolved Cu, Zn, Mn, Cr, Ni, Cd, and As were analysed for the period 1988-2001. The obtained mean values show that this contribution, both because of the magnitude of total metals (895.1 kg/h), composition, toxicity (8.7 kg/h of As+Cd+Pb) and persistence, is an incomparable case in heavy metal contamination of estuaries. The amount and typology of heavy metal discharge to the Ria of Huelva are related to freshwater flow (and, consequently, to rainfall); as a result, two different types of heavy metal discharge can be distinguished in the estuary: during low water (50% of the days), with only 19.3 kg/h of heavy metals, and during high water or flood (17% of the days), where daily maximum discharge of 72,475 kg of heavy metals were recorded, from which 1481 kg were of As, 470 kg of Pb, and 170 kg of Cd. In the most frequent situation (77% of the days), the Odiel River discharges from 90% to 100% of the freshwater received by the estuary. Despite this, the high concentration of heavy metals in the Tinto River water causes this river to discharge into the Ria of Huelva 12.5% of fluvial total dissolved metal load received by the estuary.     

墨水湖上覆水与沉积物间隙水中重金属的分布特征

武汉市墨水湖重金属污染严重，在我国内陆城市受污染湖泊中具代表性。应用 ICP MS对墨水湖上覆水和沉积物间隙水中的主要重金属元素进行了定量测试，并分析了其空间分布特征和变化规律。在此基础上，结合微量重金属界面扩散通量的计算，定量评估了其对上覆湖水水质的影响，以期为浅水湖泊的重金属污染防治提供科学依据。研究结果表明，墨水湖沉积物间隙水中重金属的浓度由高到低依次为：Mn>Fe>Zn>Cu>Cr>Pb；上覆水和沉积物间隙水中微量重金属浓度剖面均表现出明显相似的峰形分布特征，指示了湖泊沉积物中普遍存在微量重金属的沉积后再迁移现象；Fe和Mn在间隙水中的浓度远大于它们在上覆水中的浓度，其剖面分布特征主要是参与氧化还原反应的结果，Cu、Cr、Pb和Zn等的浓度也因受氧化还原过程及矿物平衡作用的影响而波动；微量重金属元素按照浓度梯度经孔隙水从沉积物向上覆水中扩散，并最终影响上覆水.     

Bioavailability of sediment-associated and low-molecular-mass species of radionuclides/trace metals to the mussel Mytilus edulis

Sediments can act as a sink for contaminants in effluents from industrial and nuclear installations or when released from dumped waste. However, contaminated sediments may also act as a potential source of radionuclides and trace metals to the water phase due to remobilisation of metals as dissolved species and resuspension of particles. The marine mussel Mytilus edulis is a filter-feeding organism that via the gills is subjected to contaminants in dissolved form and from contaminants associated to suspended particles via the digestive system. In this paper the bioavailability of sediment-associated and seawater diluted Cs, Co, Cd and Zn radioactive tracers to the filtering bivalve M. edulis has been examined. The mussels were exposed to tracers diluted in ultrafiltered (<10 kDa) seawater (Low Molecular Mass form) or to tracers associated with sediment particles from the Stepovogo Fjord at Novaya Zemlya in short-term uptake experiments, followed by 1-month depuration experiments in flow-through tanks. A toxicokinetic model was fitted to the uptake and depuration data, and the obtained parameters were used to simulate the significance of the two uptake pathways at different suspended sediment loads and sediment-seawater distribution coefficients. The results of the model simulations, assuming steady state conditions, suggest that resuspended particles from contaminated sediments can be a highly significant pathway for mussels in the order ¹⁰⁹Cd ≌ ⁶⁵Zn < ¹³⁴Cs < ⁶⁰Co. The significance increases with higher suspended sediment load and with higher K_d. Furthermore, the experimental depuration data suggest that Cs is retained longer and Co, Cd and Zn shorter by the mussels when associated with ingested sediments, than if the metals are taken up from the low molecular mass (LMM) phase.     

Particulate and dissolved elemental loads in the Kuji River related to discharge rate

In order to investigate influences of discharge rates on fluvial transport behavior of elements in the Kuji River, Japan, suspended and dissolved phase concentrations in the river water were measured together with the water flow rates. The concentrations of suspended particulate matter (SPM) increased by two or three orders of magnitude with the water discharge, and also had seasonal variations. Adsorptive elements or heavy metal elements, which tend to form insoluble compounds, were present generally as suspended forms in the river waters, and their dissolved form concentrations tended to increase with the water discharge. On the other hand, non-adsorptive elements such as alkali and alkaline-earth elements were present as dissolved forms under a normal flow rate condition, but equivalent quantity of suspended species also occurred under a high flow condition. In this case, the dissolved form concentrations decreased with the water discharge. Characterization of SPM with analyses of chemical compositions, scanning electron microscopy (SEM) and X-ray diffractometry (XRD) indicated that clay mineral such as montmorillonite would be the main carrier material of trace and major elements during the fluvial transport in the Kuji River. Variations of contents of selected elements in SPM with the water discharge indicated that river bottom sediments, which are probably potential sources of SPM added due to high water flow rates, would be different in chemical compositions from SPM floating under a normal flow condition. Variations of chemical compositions of SPM as well as of suspended or dissolved form concentrations of elements in the river waters were formulated as a function of the water discharge rates.     

长江口洋山海域表层沉积物重金属的富积及其潜在生态风险评价

根据长江口洋山海域表层沉积物监测资料,利用变异系数法和富积系数法,对表层沉积物中重金属的空间波动程度及富积程度进行了分析,并采用Hakanson潜在生态危害指数法对其潜在生态危害程度进行了评价.结果表明:在表层沉积物所监测的重金属中,Pb元素的空间波动程度最高,其它重金属元素的空间波动程度较低,各重金属空间波动程度的顺序依次为Pb＞Cd＞Hg＞Cu＞Cr＞As＞Zn;沉积物中Cu元素的富积程度最高,Pb元素次之,其它重金属元素的富积程度较低,各重金属富积程度的顺序依次为Cu＞Pb＞Zn＞As＞Cr＞Cd＞Hg.潜在生态危害评价结果显示:洋山海域表层沉积物中的重金属对海洋生态系统的潜在生态危害较轻微,均属于轻微潜在生态危害程度,其轻微潜在生态危害程度顺序为Cu＞As＞Hg＞Pb＞Cd＞Cr＞Zn.     

Spatial variations of heavy metals contamination in sediments from Odiel river (Southwest Spain)

The presence of heavy metal concentrations was examined in surface sediments from 27 sites within the Odiel river in the southwest Spain suffering inputs from industrial and mining activities. The interest is specially focused on the final delta located in the Odiel Natural Park, which constitutes a feeding ground of international importance for migrating birds. The behavior of 10 heavy metals (Zn, Cd, Pb, Cu, Cr, Mn, Ni, Fe, Hg) is conditioned by chemical properties of sediments such as acidity and carbonate or the presence of sulfate Very acidic sediments in the medium course of river contribute to the lower presence of metal as a consequence of leaching process. However, tidal action raises the pH in the marshes of the delta with correlative metal accumulation. In accordance with the Müller [Umschan 79 (1979) 133-149] scale for geoaccumulation index, the entire watercourse could be considered polluted by Zn and Pb, while Cu exhibits a high presence in the delta marshes of the river.