Effects of geothermal effluents on aquatic ecosystems

The use of geothermal energy for electrical generation and a variety of other purposes requires the handling and disposal of large volumes of geothermal fluids. These fluids contain constituents such as dissolved ammonia, hydrogen sulfide gas, and trace elements. Facilities in the United States are not expected to routinely discharge large volumes of toxic geothermal fluids. However, chronic effects on aquatic ecosystems are possible at concentrations where acute toxicity would be neither expected nor observed. Also, some trace elements may accumulate to hazardous levels in ecosystems, even when released at nontoxic concentrations.     

The chemistry of the Beavon sulfur removal process

The Beavon Sulfur Removal Process (BSRP) removes essentially all of the sulfur compounds from Claus plant tail gases. The sulfur containing compounds, such as hydrogen sulfide, sulfur dioxide, carbonyl sulfide and carbon disulfide, are converted to sulfur in over 99.9% efficiency. The BSRP consists of two stages. In the first stage the various sulfur compounds are either hydrogenated or hydrolyzed to give hydrogen sulfide while in the second stage the hydrogen sulfide is oxidized using the Stretford process to give elemental sulfur of good quality. The process is a commercial success with 29 plants operating or under construction in the United States and 4 in Japan. This process can also be utilized in Synthetic Natural Gas plants, natural gas processing, and other similar applications.     

Comparison of the chromotropic acid and modified pararosaniline methods for the determination of formaldehyde in air

Follow-up tests were performed in 25 complaint homes previously investigated by the Wisconsin Division of Health to determine ambient formaldehyde concentrations. Four collection methods were compared in each home: (1) midget impingers containing double-distilled water and immersed in ice baths, (2) midget impingers containing 1% sodium bisulfite solution and immersed in ice baths, (3) midget impingers containing cold 1% sodium bisulfite solution (temperature not maintained with an ice bath), and (4) a refrigerated, complete sampling unit developed at Lawrence Berkley Laboratory which utilized double-distilled water as a collection medium. Air was drawn through the midget impingers using personal sampling pumps. All four types of sampling trains were operated simultaneously in a bedroom, collecting specimens within an area of about 4 ft², while in the kitchen or living room, all sampling trains except for the impingers containing 1% sodium bisulfite solution and immersed in ice baths were operated together. Analysis of variance indicated that the three samples collected using midget impingers and personal sampling pumps gave similar results. All specimens collected in water were analyzed using both the chromotropic acid and pararosaniline analytical methods. Quality control specimens prepared in the laboratory showed excellent agreement between the two methods; however, field specimens through which air had been drawn were assigned lower values using the pararosaniline method. Special precautions were taken to ensure that specimens collected in water were not contaminated with sodium bisulfite, a serious interference for the pararosaniline test. To rule out the possibility that specimens deteriorated between analysis, test results from each method were confirmed by repeating each method for selected sets of specimens for a period of several days. It was hypothesized that some source of interference was present in the field specimens which affected the pararosaniline analysis. Statistical tests were applied to determine whether the observed discrepancy between the analytical methods was consistent and a regression model was employed to determine whether any of the other environmental parameters measured during sample collection was associated with the discrepancy.     

Determination of low (137)Cs concentration in seawater using ammonium 12-molybdophosphate adsorption and chemical separation method

A new method has been developed for analyzing (137)Cs in a small volume of seawater. Ammonium 12-molybdophosphate (AMP) was used two times during pretreatment procedure. The first step was to adsorb (137)Cs in seawater samples into AMP in order to reduce sample volume, and the second was to remove (87)Rb, interference nuclide for beta counting. The AMP adsorbing (137)Cs was dissolved by sodium hydroxide solution, and then (137)Cs was finally formed to be cesium chloroplatinate precipitate by adding 10% hexachloroplatinic acid. The beta rays emitted from (137)Cs were measured with a low background gas-proportional alpha/beta counter. This method was applied to several seawater samples taken in the East Sea of Korea. Compared to the routinely used gamma-spectrometry method, this new AMP method was reliable and suitable for analyzing (137)Cs in deep seawater.     

南京城区黑臭河道底泥污染特征及生态风险评价

河道黑臭是目前我国许多城市面临的环境问题,研究其底泥中的污染物如有机质、氮磷和重金属的污染特征并据此进行生态风险评价,对城市黑臭河道的污染控制与生态修复具有十分重要的意义。选取南京城区内8条典型黑臭河道,采集其表层底泥样品进行分析,测得其中有机质、总氮、总磷的含量分别为0.75%～10.86%、0.05%～0.68%、0.04%～0.23%,三者之间呈显著正相关关系,表明了它们较好的同源性,应用沉积物质量标准评价发现,这3种污染物污染程度总体介于严重级与最低级之间,但氮磷的污染比有机质更为严重。底泥中6种重金属的平均含量均超过背景值,相关性分析结果表明Cu、Cr、Ni、Zn之间均呈极显著正相关关系,而重金属与营养物之间未发现较好的相关性,潜在生态风险评价结果表明底泥中重金属污染严重,84.2%的河道具有高潜在生态风险,各元素的潜在生态风险顺序依次为 Cd >Cu >Pb >Cr >Ni >Zn,Cd为主要污染物,具有很高潜在生态风险。与国内其他典型受污染水体相比,南京城区黑臭河道底泥中总氮、总磷与重金属Cd的污染更为严重。     

溪洛渡水电工程拦沙对三峡水库富营养化潜在影响的初步研究

从泥沙吸附的角度，探讨金沙江溪洛渡水电站拦沙对三峡水库溶解性磷负荷的影响。2006年11月在金沙江、长江干流和支流岷江、沱江采集了淤积泥沙和水样，测定了泥沙的全磷、有效磷和磷固定量及水的溶解性磷等指标。岷江和沱江泥沙的有效磷含量远高于金沙江和长江干流，反映了四川盆地支流的磷污染较干流严重；干流泥沙的有效磷含量向下游呈增加和磷固定量向下游呈减少的趋势，反映了干流泥沙沿途不断吸附四川盆地支流汇入干流中的溶解性磷，磷固定能力有所降低。根据金沙江宜宾与长江朱沱泥沙的有效磷含量和磷固定量，金沙江来沙年吸附溶解性磷分别为382和6 885 t，分别相当于朱沱站的26%和468％。溪洛渡水库拦蓄泥沙，金沙江来沙吸附长江干流溶解性磷的量将有所减少。水库投入运行后的前50年，以有效磷含量计，金沙江来沙的磷吸附量占朱沱年溶解性磷总量的比例从26%降至10%；以磷固定量计，从468％降至174%。长江干流进入三峡水库的年溶解性磷总量有可能增加16%～294%。金沙江来沙降低三峡入库磷负荷的实际功能，可能介于有效磷含量和磷固定量的计算值之间，具体值还需开展进一步的试验研究。     

A bioassay approach to determine the dioxin-like activity in sediment extracts from the Danube River: ethoxyresorufin-O-deethylase induction in gill filaments and liver of three-spined sticklebacks (Gasterosteus aculeatus L.)

Sediment samples from the upper Danube River in Germany have previously been characterized as ecotoxicologically hazardous and contaminants in these sediments may contribute to the observed decline of fish populations in this river section. For the investigation of sediment toxicity there is a need for development, standardization and implementation of in vivo test systems using vertebrates. Therefore, the main objective of this study was to apply and evaluate a recently established fish gill EROD assay as a biomarker in sediment toxicity assessment by using extracts of well characterised sediment samples from the upper Danube River. This to our knowledge is the first application of this novel assay to sediment extracts. Sediments from four different sites along the upper Danube River were Soxhlet-extracted with acetone and dissolved in DMSO. Three-spined sticklebacks (Gasterosteus aculeatus L.) were exposed for 48 h to various concentrations of the extracts, to the positive control beta-naphthoflavone or to the solvent. Measurements of EROD activity in gill filaments and liver microsomes followed the exposure. Concentration-dependent induction of EROD in both gill and liver was found for all sediment extracts. The highest EROD-inducing potency was determined for extracts of sediments from the sites "Opfinger See" and "Sigmaringen" and the EROD activities in gill and liver correlated well. The results from the gill and liver assays were in accordance with in vitro results of previous investigations. The EROD activities measured in the present study corresponded with the concentrations of PAHs, PCBs and PCDD/Fs in the sediment samples derived in a previous study. The sticklebacks in this study were in the reproductive phase and a stronger EROD induction was obtained in the females than in the males. Implementation of the EROD assay in testing of sediment extracts gave highly reliable results which make this assay an ecotoxicologically relevant method for assessment of contamination with Ah receptor agonists in sediments.     

丹江流域水沙变化特征分析

丹江流域是南水北调中线工程重要水源地,近年来受多种因素影响,径流泥沙情况发生了很大变化,准确把握其变化趋势对水资源管理及水土保持工作意义重大。该文基于荆紫关水文站1958～2015年径流和悬移质输沙量资料,运用Mann-Kendall 检验法、距平累积法、滑动t检验法以及双累积曲线法,阐明了丹江流域近60年径流量和悬移质输沙量变化特征,定量分析了各影响因素在径流泥沙变化中的作用。结果表明：丹江流域径流量与悬移质输沙量年际变化大,呈显著下降趋势,1958～1972、1982～1989年为丰水丰沙期,1972～1981年与1990～2015年处于枯水枯沙期,径流量和悬移质输沙量分别在1983年与1989年发生突变。人为因素和降水的贡献率分别为58.8%和41.2%,说明人为因素特别是水利水土保持工程是引起丹江流域输沙变化的主要因素。     

Sediment budgets and source determinations using fallout Cesium-137 in a semiarid rangeland watershed,Arizona, USA

Analysis of soil redistribution and sediment sources in semiarid and arid watersheds provides information for implementing management practices to improve rangeland conditions and reduce sediment loads to streams. The purpose of this research was to develop sediment budgets and identify potential sediment sources using ¹³⁷Cs and other soil properties in a series of small semiarid subwatersheds on the USDA ARS Walnut Gulch Experimental Watershed near Tombstone, Arizona, USA. Soils were sampled in a grid pattern on two small subwatersheds and along transects associated with soils and geomorphology on six larger subwatersheds. Soil samples were analyzed for ¹³⁷Cs and selected physical and chemical properties (i.e., bulk density, rocks, particle size, soil organic carbon). Suspended sediment samples collected at measuring flume sites on the Walnut Gulch Experimental Watershed were also analyzed for these properties. Soil redistribution measured using ¹³⁷Cs inventories for a small shrub-dominated subwatershed and a small grass-dominated subwatershed found eroding areas in these subwatersheds were losing −5.6 and −3.2 t ha⁻¹ yr⁻¹, respectively; however, a sediment budget for each of these subwatersheds, including depositional areas, found net soil loss to be −4.3 t ha⁻¹ yr⁻¹ from the shrub-dominated subwatershed and −0.1 t ha⁻¹ yr⁻¹ from the grass-dominated subwatershed. Generally, the suspended sediment collected at the flumes of the six other subwatersheds was enriched in silt and clay. Using a mixing model to determine sediment source indicated that shrub-dominated subwatersheds were contributing most of the suspended sediment that was measured at the outlet flume of the Walnut Gulch Experimental Watershed. The two methodologies (sediment budgets and sediment source analyses) indicate that shrub-dominated systems provide more suspended sediment to the stream systems. The sediment budget studies also suggest that sediment yields measured at the outlet of a watershed may be a poor indicator of actual soil redistribution rates within these semiarid watersheds. Management of these semiarid rangelands must consider techniques that will protect grass-dominated areas from shrub invasion to improve rangeland conditions.     

Separation and measurement of thorium, plutonium, americium, uranium and strontium in environmental matrices

A technique for the isolation of thorium (Th), plutonium (Pu), americium (Am), uranium (U) and strontium (Sr) isotopes from various environmental matrices has been adapted from a previously published method specific to water samples (Maxwell, 2006). Separation and isolation of the various elemental fractions from a single sub-sample is possible, thereby eliminating the need for multiple analyses.The technique involves sample dissolution, concentration via calcium phosphate co-precipitation, rapid column extraction using TEVA™, TRU™ and Sr-Spec™ resin cartridges, alpha spectrometry for Th, Pu, U and Am and Cerenkov counting for Sr.Various standard reference materials were analysed and chemical yields are in the range of 70-80% for Th, Am, U and Sr and 50-60% for Pu. Sample sizes of up to 10 L for water, 5 g for dry soil and sediment and 10 g for dry vegetation and seaweed can be processed using this technique.     

Perfluoroalkyl substances and extractable organic fluorine in surface sediments and cores from Lake Ontario

Fourteen perfluoroalkyl substances (PFASs) including short-chain perfluorocarboxylates (PFCAs, C4–C6) and perfluoroalkane sulfonates (PFSAs, C4 and C6) were measured in surface sediment samples from 26 stations collected in 2008 and sediment core samples from three stations (Niagara, Mississauga, and Rochester basins) collected in 2006 in Lake Ontario. Perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), and perfluoroundecanoate (PFUnDA) were detected in all 26 surface sediment samples, whereas perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonamide (FOSA), perfluorododecanoate (PFDoDA) and perfluorobutanoate (PFBA) were detected in over 70% of the surface sediment samples. PFOS was detected in all of the sediment core samples (range: 0.492–30.1 ng g^− 1 d.w.) over the period 1952–2005. The C8 to C11 PFCAs, FOSA, and PFBA increased in early 1970s. An overall increasing trend in sediment PFAS concentrations/fluxes from older to more recently deposited sediments was evident in the three sediment cores. The known PFCAs and PFSAs accounted for 2–44% of the anionic fraction of the extractable organic fluorine in surface sediment, suggesting that a large proportion of fluorine in this fraction remained unknown. Sediment core samples collected from Niagara basin showed an increase in unidentified organic fluorine in recent years (1995–2006). These results suggest that the use and manufacture of fluorinated organic compounds other than known PFCAs and PFSAs has diversified and increased.     

基于AnnAGNPS模型的三峡库区小江流域非点源污染负荷评价

运用AnnAGNPS模型对三峡库区小江流域2002～2004年的径流量、输沙量、氮磷负荷量进行模拟估算,并分别采用宝塔窝水文站（控制范围占流域面积的62%）2002～2004年实测数据对径流和泥沙模拟值进行校准和验证,采用小江流域出口2002～2004年实测年均数据对总氮、总磷模拟负荷进行校准和验证,通过敏感性分析确定了影响流域非点源污染负荷输出的主要因子,结果表明模型模拟结果相对可靠,适合于三峡库区流域非点源污染负荷评价。根据模型预测结果,模型对径流输出的模拟精度高于对泥沙和养分的输出模拟,小江流域多年年均泥沙输出量为26189 万t,总氮输出为8 33523 t,总磷输出为43686 t。研究成果对于AnnAGNPS模型在三峡库区的应用具有很好的示范性     

Determination of technetium-99 using electrothermal vaporization inductively coupled plasma-mass spectrometry (ETV-ICP-MS) and NH4OH as chemical modifier

In recent years, developments in ICP-MS have led to improved methods for determination of long-lived radionuclides. This paper reports the use of NH(4)OH as a matrix modifier and ETV sample introduction for the determination of technetium-99 ((99)Tc) in a variety of environmental and biological samples, using Re as carrier and (99m)Tc as yield monitor in the chemical separation method. Addition of an excess of NH(4)OH led to a stable (99)Tc signal, reduced memory effect, better reproducibility and reduced detection limits. Following radiochemical separation of (99)Tc from the sample matrix, detection limits in the order of a few microBq have been achieved. ETV has also proved applicable for rapid, direct analysis of a number of environmental samples having relatively high concentrations of (99)Tc (sediment extracts and river water close to nuclear installations). However, in this case, control of matrix effects (signal reduction and enhancement) using standard additions is necessary.     

Natural radionuclides as tracers of the dispersal of dredge spoil dumped at sea.

Monitoring large (underwater) surfaces, with rapidly varying composition, requires a sampling density which exceeds the capabilities of standard techniques. These techniques involve sample collection and a number of treatments and measurements in the laboratory; both steps are laborious, tedious and costly. This paper presents an in situ method in which a detector system is trailed over the surface and measures continuously the gamma rays emitted by the natural radionuclides in the sediment. Since each sediment component has its own characteristic set of activity-concentration values (radiometric fingerprint), the composition of the sediment can be deduced quantitatively. This paper shows the application of this technique for monitoring the dispersal of dredge spoil from Rotterdam harbour, dumped in the North Sea. In addition to a qualitative picture of dredge spoil dispersal, a mass balance equation has been used to quantitatively assess the dredge spoil transport with time.     

长江大通站输沙量时间序列分析研究

长江来水来沙直接影响着河口三角洲的发育过程以至入海物质通量变化。大通站作为长江河口的第一个关键界面,有近50年左右的输沙量和流量连续观测资料（1953~2001年）。利用肯德尔、有序聚类和熵谱分析等方法,着重对输沙量时间序列进行了统计分析。大通站径流量在保持稳定的情势下,输沙量在过去49年中有明显的下降。输沙量变化主要呈跳跃式下降,同时表现出16年左右周期性阶梯下降规律,1968年和1984年分别为阶梯下降的跳跃点。尤其1984年后,年均输沙量比1984年前下降26.4％,且最大值未超过1984年前的平均值。输沙量减少与人类活动密切相关。20世纪80年代末的“长江上游水土保持重点防治工程”的实施,使长江上游的来沙减少,这是大通站输沙量减少的主要原因;其次是长江流域内水利工程的拦沙作用。     

基于遥感反演长江中游地区悬浮泥沙研究

悬浮泥沙定量研究对于调查长江的水质、地貌、生态环境等起着至关重要的作用。以长江中游武汉地区2012~2013年14幅不同时相的Landsat ETM+遥感影像为主要数据源,结合野外采样悬浮泥沙浓度数据,分析了悬浮泥沙遥感定量反演方法,数据处理中针对ETM+SLC OFF影像缝隙问题,采用自适应局部回归匹配算法（ALR）进行影像自动恢复处理,在波段选择中对悬浮泥沙浓度和光谱反射率数据进行相关性分析,并运用传统关系建模方法和高斯模型方法对比,比较悬浮泥沙定量反演模型,利用实测验证数据对反演模型精度进行评估。研究结果表明：（1）ALR可以有效的获取悬浮泥沙敏感波段的遥感光谱反射率;（2）ETM+Band3悬浮泥沙浓度的高斯模型相关系数最高,通过对比得到模型反演的验证精度较高,研究证明遥感定量反演适合于长江流域武汉段泥沙含量大范围监测     

Remobilisation of 109Cd, 65Zn and 54Mn from freshwater-labelled river sediments when mixed with seawater

A major fraction of trace metals transported by rivers is associated with sediments, especially during flooding, when erosion and resuspension increase sediment loads. Upon contact with seawater in estuaries, changes in ionic strength and pH may remobilise trace metals from sediment surfaces into more bioavailable forms. The objective of the present work was to investigate time-dependent interactions between trace metals and freshwater sediments and their potential remobilisation upon contact with seawater. Two river sediments (one organic and one inorganic) were labelled with 109Cd2+, 65Zn2+ and 54Mn2+ radioactive tracers for periods up to 6 months. Sorption of tracers occurred rapidly (> or = 80% sorption, < 1 h), followed by a slower approach to pseudoequilibrium. Kd(6 months) were estimated as 460, 480 and 2200 ml/g (inorganic sediment) compared to 5300, 4000 and 1200 ml/g (organic sediment) for 109Cd, 65Zn and 54Mn, respectively. Remobilisation of tracers from labelled sediments was studied using sequential extractions. Artificial seawater extracts simulated an estuarine environment. Subsequent extractions provided information about more strongly sorbed tracer fractions within sediments. Remobilisation of 109Cd by seawater was significant (> 65%) and least affected by sediment type or freshwater labelling time. Redistribution of Cd to strongly bound phases was minimal (4% and 1% of 109Cd in strongly oxidisable fractions). Seawater remobilisation of 65Zn was significantly greater from the organic sediment (54%) compared to the inorganic sediment (8%), where a large fraction of 65Zn (14%) became irreversibly bound. Similarly, more 54Mn was remobilised by seawater from the organic sediment than the inorganic sediment (66% and 3% remobilised, respectively), i.e., 54Mn became more strongly bound in the inorganic sediment. A simple three-box model, based on first-order differential equations, was used to describe the interaction between tracers in spiked freshwater and two operationally defined sediment fractions ("seawater exchangeable" and "seawater unexchangeable") up to 6 months of freshwater labelling. Model simulations were fitted to experiment data and apparent rate constants were calculated using numerical optimisation methods. Sorption ratios from modelling data (i.e., k1/k2) were greater for organic compared to inorganic sediments, while fixation ratios were higher in inorganic sediments. In conclusion, trace metals can be remobilised from sediments on contact with seawater in estuaries. High organic content in sediments increased initial sorption of tracers but inhibited redistribution to more strongly bound fractions over time, resulting in greater remobilisation of tracers when in contact with seawater.     

Sulfide production during anaerobic lagoon treatment of tapioca wastewater

Laboratory-scale experiments on anaerobic lagoon treatment of tapioca wastewater were conducted under ambient, tropical conditions. The objectives of this study were to investigate factors that affect hydrogen sulfide production and to propose means to control the formation of hydrogen sulfide in lagoon effluents. The concentrations of sulfides were found to increase with increasing organic loading from 2.76 to 5.77 kg COD/m³.d, decreasing hydraulic retention time; and increasing pH from 3 to 7. The maximum total sulfide concentration of 18.8 mg/L occurred at the organic loading of 5.77 kg COD/ m³.d and neutral pH. the maximum H₂S concentration was calculated to be 13.3 mg/L which occurred in the laggoon operated at an organic loading of 5.77 kg COD/m³.d and a pH of 5. The control of odour problems due to the H₂S formation should be possible by raising pH of the lagoon water to be more than 8 or operating the lagoon at low organic loadings.     

溪洛渡水电工程拦沙对三峡水库富营养化潜在影响的初步研究

从泥沙吸附的角度,探讨金沙江溪洛渡水电站拦沙对三峡水库溶解性磷负荷的影响。2006年11月在金沙江、长江干流和支流岷江、沱江采集了淤积泥沙和水样,测定了泥沙的全磷、有效磷和磷固定量及水的溶解性磷等指标。岷江和沱江泥沙的有效磷含量远高于金沙江和长江干流,反映了四川盆地支流的磷污染较干流严重;干流泥沙的有效磷含量向下游呈增加和磷固定量向下游呈减少的趋势,反映了干流泥沙沿途不断吸附四川盆地支流汇入干流中的溶解性磷,磷固定能力有所降低。根据金沙江宜宾与长江朱沱泥沙的有效磷含量和磷固定量,金沙江来沙年吸附溶解性磷分别为382和6 885 t,分别相当于朱沱站的26%和468％。溪洛渡水库拦蓄泥沙,金沙江来沙吸附长江干流溶解性磷的量将有所减少。水库投入运行后的前50年,以有效磷含量计,金沙江来沙的磷吸附量占朱沱年溶解性磷总量的比例从26%降至10%;以磷固定量计,从468％降至174%。长江干流进入三峡水库的年溶解性磷总量有可能增加16%～294%。金沙江来沙降低三峡入库磷负荷的实际功能,可能介于有效磷含量和磷固定量的计算值之间,具体值还需开展进一步的试验研究。     

Uranium in sediments, mussels (Mytilus sp.) and seawater of the Krka river estuary

The response of an aquatic environment to the decrease of phosphate discharges from a technologically improved transhipment terminal, situated at the Croatian Adriatic coast in the port of Sibenik, has been assessed based on uranium activity and concentration in sediment, seawater and mussels Mytilus sp. The highest 238U activities (485+/-16Bqkg(-1) dry weight) were found in the sediment sample collected from the sampling site closest to the terminal. The maximum concentrations in the sediment samples are above the natural ranges and clearly indicate the harbour activities' influence. The 238U/226Ra activity ratios in sediment samples demonstrate the decreasing trend of phosphate ore input. Mussel samples showed levels of 238U activities in the range from 12.1+/-2.9 to 19.4+/-7.2 Bqkg(-1) dry weight, thus being slightly higher than in normally consumed mussels. Only the seawater, taken just above the bottom sediment at the sampling site closest to the terminal, shows a slightly higher uranium concentration (3.1+/-0.2 microgL(-1)) when compared to the samples taken in upper seawater layers (2.1+/-0.2 microgL(-1)) but is in the range of the concentration level of uranium in natural seawater. Since the transhipment terminal in the port of Sibenik was modernised in 1988, discharge of phosphate ore into the seawater was drastically reduced and, consequently, uranium concentration levels in seawater have decreased. However, enhanced uranium activity levels are still found in deeper sediment layer samples and in mussel.