有机质对城市污染河道沉积物铵态氮吸附-解吸的影响

采集污染程度不同的城市河道沉积物(通吕运河、濠河和通甲河),在分析H2O2对沉积物有机质和铵态氮影响的基础上,分析沉积物在去除有机质前后铵态氮释放动力学和吸附热力学过程,研究城市污染河道沉积物有机质对铵态氮吸附-解吸的影响.结果表明:单位体积H2O2对有机质去除率随H2O2使用量增多而降低;去除有机质后,沉积物铵态氮含量显著增加,通吕运河、濠河和通甲河铵态氮最大含量分别是有机质去除前的4.16、3.55和2.85倍;沉积物对铵态氮的饱和吸附量随有机质含量减少而下降;沉积物铵态氮释放过程均表现为先快速释放,后减缓至平衡过程;去除有机质后,随着有机质含量的减少,沉积物铵态氮的最大释放量呈增大趋势;沉积物有机质和铵态氮含量是影响沉积物铵态氮释放的主要因素.     

Influence of the pore structure and surface chemical properties of activated carbon on the adsorption of mercury from aqueous solutions

Reactivation and chemical modification were used to obtain modified activated carbons with different pore structure and surface chemical properties. The samples were characterized by nitrogen absorption–desorption, Fourier transform infrared spectroscopy and the Bothem method. Using mercury chloride as the target pollutant, the Hg²⁺ adsorption ability of samples was investigated. The results show that the Hg²⁺ adsorption capacity of samples increased significantly with increases in micropores and acidic functional groups and that the adsorption process was exothermic. Different models and thermodynamic parameters were evaluated to establish the mechanisms. It was concluded that the adsorption occurred through a monolayer mechanism by a two-speed process involving both rapid adsorption and slow adsorption. The adsorption rate was determined by chemical reaction.     

电极材料对电化学改性无烟煤前后甲烷吸附解吸特性影响的实验研究

针对电化学作用能够显著增强煤中甲烷解吸渗流特性,但对其电极材料的选择缺乏依据的问题,采用实验的方法研究了铝、铁、铜和石墨四种电极材料对电化学改性无烟煤甲烷吸附解吸特性的影响.结果表明：（1）未改性自然煤样的甲烷饱和吸附量a为39.92 mL·g^-1,由铝、铁、铜和石墨四种电极材料进行电化学改性后阳极区域煤样的甲烷饱和吸附量a分别降低了5.22%、8.48%、9.24%和11.33%,阴极区域煤样的甲烷饱和吸附量a分别降低了9.53%、4.97%、6.25%和4.97%;（2）未改性自然煤样在300 min的甲烷解吸率为83.17%,经铝、铁、铜和石墨四种电极材料改性后阳极区域煤样的甲烷解吸率分别提高了9.50%、7.10%、8.36%和15.75%,阴极区域煤样的甲烷解吸率分别提高了1.76%、1.12%、6.10%和16.23%;（3）采用石墨作为电极的电化学对无烟煤甲烷解吸的影响效果最为明显,原因在于石墨阳极处电解反应生成较多的H⁺离子,一方面对煤表面进行酸化,抑制了煤甲烷的吸附,另一方面更多地溶蚀煤中的碳酸盐和硫酸盐矿物,增加了煤中的孔隙,使得甲烷最终解吸率有所升高.本文的研究结果可为电化学强化煤甲烷解吸电极材料的优选提供基础依据.

     

北京市北运河沉积物对氮、磷的吸附/解吸动力学特征

选取北运河土沟、榆林庄及和合站3个典型河道断面,进行河道0~60 cm深度沉积物对氨氮、磷酸盐的吸附/解吸批平衡静态试验研究,采用多种动力学模型分析北运河沉积物对氮、磷的吸附/解吸动力学特性,提出适用于北运河沉积物吸附/解吸特性的动力学模型,并对模型参数的主要影响因素进行探讨.结果表明:1)北运河典型断面各深度的沉积物对氨氮和磷酸盐的吸附/解吸过程总体呈现3个阶段:快反应阶段—慢反应阶段—平衡阶段;在0~0.5 h的快反应阶段可完成吸附或解吸总量的60%,且对氮、磷的吸附速率大于解吸速率.2)北运河各断面对氨氮与磷酸盐的平衡吸附量表现为S(榆林庄)S(土沟)S(和合站);对氨氮的平衡解吸量表现为S(土沟)S(榆林庄)S(和合站),对磷酸盐的平衡解吸量表现为S(和合站)S(土沟)S(榆林庄),沉积物对氨氮和磷酸盐的吸附以化学吸附为主,平衡吸附与解吸量随断面深度的增加而减小,0~20 cm表层沉积物对氮、磷的吸附能力较强.3)Lagergren二级动力学模型对各深度沉积物的吸附/解吸过程拟合最优,模型参数公式为k2=S-0.369max+0.163;qe=0.022 Smax+18.077 Kf+41.947.通过模拟得出在400 mg/L氮、磷浓度下吸附于沉积物中的氮、磷污染物会随着解吸过程释放52%~80%的氨氮和6%~42%的磷酸盐,可能不仅二次污染上覆水体,还随河水下渗从而对地下水质形成潜在污染风险.     

The distribution of mercury in the surficial sediments of the northern Tyrrhenian sea

Marine sediments are the ultimate recipient of mercury introduced into aquatic ecosystem either by man or by weathering. In the surficial sediments of the northern Tyrrhenian sea high concentrations of this metal were found in an area close to the effluent of a chlor-alkali plant and in the bays of La Spezia and Leghorn, which receive wastes from numerous industries and from port activities.The sediments of a much larger marine area off the mouths of the Ombrone, Albegna and Fiora rivers also contain high levels of Hg, part of which derives from the weathering of the rich cinnabar deposits of Mount Amiata and part from mining and processing the cinnabar.     

The role of sulphide in the formation of dimethyl mercury in river and estuary sediments

The role of sulphide-containing species in sediments in the mobilization of mercury in the environment is demonstrated. The mobile species is the volatile hydrophobic dimethyl mercury. Transport to atmosphere in this form may account for a loss of about 12% annually of methyl mercury from sediments and may therefore be a substantive part of the biogeochemical cycling of mercury in the environment.     

滇池表层沉积物铵态氮吸附特征

为研究滇池内源污染特征,2013年利用GIS软件针对滇池全湖布设36个采样点,采集表层沉积物,研究滇池表层沉积物铵态氮(NH_4+-N)吸附特征,同时分析沉积物的理化性质对NH_4+-N吸附特性的影响.结果表明:滇池表层沉积物对NH_4+-N的吸附量在前2 h之内呈增长趋势,吸附速率较大,之后沉积物对NH_4+-N的吸附量不随时间变化而变化,基本达到平衡,最大吸附速率均发生在0~5 min内;不同区域表层沉积物NH_4+-N最大吸附速率平均值表现为:外海南部湖心区外海北部草海,最大吸附量平均值表现为:湖心区外海南部外海北部草海,吸附效率平均值表现为:外海北部草海湖心区外海南部;沉积物对NH4+-N的吸附量与NH_4+-N的初始浓度大致呈线性关系,并且低浓度下表现出很好的吸附/解吸特征;滇池表层沉积物NH_4+-N的吸附解吸平衡浓度(ENC0)高于上覆水中NH_4+-N浓度,表明沉积物中NH_4+-N有向上覆水中释放的风险,沉积物在很长一段时间内起到水体污染"源"的作用;ENC0与沉积物中总氮、NH_4+-N含量呈显著正相关,本底吸附量和有机质总量呈显著负相关,沉积物吸附NH_4+-N主要受有机质的影响.     

Physical and chemical characterization of sediments from an Andean river exposed to mining and agricultural activities: The Moquegua River,Peru

This study presents an analysis of sediments in an Andean river impacted by both natural conditions and anthropogenic activities. Fifty samples were collected from selected sites throughout the Moquegua River drainage basin, and Tambo River headwaters at Pasto Grande, in Peru, and analysed with X-ray diffraction, energy dispersive X-ray spectroscopy, scanning electron microscopy, Fourier-transform infrared spectroscopy and thermogravimetric analysis. Si, Ca, Al, Fe, and O, common constituents of...     

The degree of trace metal pyritization in subtidal sediments of a mariculture area: application to the assessment of toxic risk

Four 2–3 m sediment cores were taken at the sites on the periphery of mussel raft concentrations in the subtidal zone of the inner Ría de Vigo (Galicia, NW Spain) with a view to evaluate the potential risk to mariculture from sediment-borne trace elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn). The distribution of each of these elements in reactive, organic, pyrite and silicate-bound fractions was determined at 64 samples, and these data were used to calculate the degree of trace metal pyritization (DTMP) of each metal/metalloid. In the top 10–20 cm, relatively oxic conditions led to As, Cd, Cu, Pb and Zn having large reactive fractions due to their association with Fe and Mn oxyhydroxides. At lower levels, anoxic conditions favoured by intense diagenesis led to the precipitation of trace metals and metalloids as sulphides, with or without association with pyrite. Particularly large pyrite fractions in the 20–100 cm layer are attributed to the organic matter of this layer being more marine in origin than that of deeper sediments. DTMP was greatest for Cu and As, and least for Pb, Zn and Cr. The risk of trace element toxicity in the event of disturbances instituting oxic conditions in these sediments is discussed.     

Total,methyl and organic mercury in sediments of the Southern Baltic Sea

Distribution of sedimentary mercury in the Southern Baltic was investigated. Sediment samples were collected from the Southern Baltic in the period from 2009 to 2011, and concentrations of sedimentary total mercury (average 102 ng/g, range 5.8–225 ng/g) and methyl mercury (average 261 pg/g, range 61–940 pg/g) were measured in the manner that the influence of both patchiness and seasonal changes were assessed. Moreover, sedimentary mercury extracted with organic solvent- the so-called organic mercury was also analyzed (average 425 pg/g, range 100–1440 pg/g). There is a statistically significant dependence between organic mercury and both methyl mercury and total mercury concentrations in the sediments. Methyl mercury contribution to total mercury varied from 0.12% to 1.05%, while organic mercury contributed to 2% of total concentration on average. The area studied, although mercury concentrations exceed threefold the geochemical background, can be regarded as moderately contaminated with mercury, and methylmercury.     

Behavioural effects of mercury on grass shrimp

Subacute exposure (0.05 ppm) to mercuric chloride significantly impairs the conditioned avoidance responses of grass shrimp Palaemonetes pugio Holthuis, when tested in an aquatic avoidance apparatus. Control animals learn to avoid a shock after the onset of a light which followed a period of dark-adaptation. A third group of shrimp, which establish an avoidance curve similar to the controls, quickly lose its ability to avoid being shocked when exposed to mercury in the final days of the experiment. These experiments demonstrate the value of a simple behavioural index for establishing subacute toxicity standards for organisms in aquatic ecocystems.     

Geochemical characteristics of phosphorus in surface sediments of two major Chinese mariculture areas: The Laizhou Bay and the coastal waters of the Zhangzi Island

Phosphorus (P) in surface sediments of the Laizhou Bay (LB) and the coastal waters around the Zhangzi Island (ZI) was analyzed. Six forms of P were separated — exchangeable or loosely sorbed P (Ads–P), aluminum-bound P (Al–P), iron-bound P (Fe–P), authigenic apatite plus CaCO₃-bound P plus biogenic apatite (Ca–P), detrital apatite plus other inorganic P (De–P) and organic P (OP). The average contents of P in the LB were in the order: De–P > OP > Ca–P > Fe–P > Ads–P > Al–P; in the ZI, the corresponding order was De–P > OP > Fe–P > Ca–P > Ads–P > Al–P. Due to the high nutrient loadings from the surrounding rivers, TP contents in sediments of the LB were higher than in those of the ZI. The potential bio-available P (Ads–P and OP) accounted for 14.7% and 24.2% of TP in sediments of the LB and the ZI, respectively.     

Characteristics of micro-interface adsorption kinetics between sediments and Cu ions

This work investigates the adsorption of Cu ions in sediments by conducting batch experiments,including isothermal experiments and adsorption kinetics experiments.Data from isothermal experiments were analyzed using the Langmuir,Freundlich and Temkin models,and the experimental kinetic data were fit using pseudo-first-order,pseudo-second-order,Elovich,liquid film diffusion and intra-particle diffusion models.The Langmuir model resulted in the best fit for the equilibrium data,which indicated that the adsorption capacity of Cu ions on the sediment was 1.0403 mg g-1 with a KL value of 4.2877 L mg-1.The Freundlich and Temkin models also provided good fits,and the nF and A values were 3.8565 and 66.9964 L mg-1,respectively,indicating stronger adsorption intensities and adsorption energies between the Cu ions and the sediment.Compared with the pseudo-first-order and Elovich models,the pseudo-second-order model was more appropriate for describing the adsorption kinetics,indicating the chemisorption nature of adsorption.The adsorption kinetic process can be divided into film diffusion,pore diffusion and adsorption reactions.The controlling step for the adsorption kinetics changed with the development of the adsorption process.The entire adsorption process took 180 min.Film diffusion was the controlling step for the first 20 min.During the 20 to 60 min period,the pore diffusion gradually increased and the film diffusion decreased so that both phenomena coexisted.Pore diffusion was the controlling step during the 60-180 min period.     

Diagenesis and bioavailability of mercury in the contaminated sediments of Ulhas Estuary, India

Sequential extraction of Hg was performed in a core collected from intertidal area in Ulhas Estuary in order to characterize the downward distribution and diagenetic behavior of Hg in a polluted estuary. Concentration of total Hg ranged between 0.46 and 6.40 μg g⁻¹ with significant decrease in surficial sediment as a result of closing of two Hg-cell based chlor-alkali plants. Results of sequential extraction showed that >65% Hg was strongly bound to organo-sulphur and inorganic sulphide species that are not bioavailable. Flux of only 18.8% of Hg was found compared to its value deposited on sediment–water interface. Hence, it is concluded that there is no significant diagenetic remobilization of Hg in Ulhas Estuary. This core also has been analyzed for ²¹⁰Pb geochronology. The estimated sedimentation rate is 0.31 cm y⁻¹ in the present sampling region.     

Impact of the chemical composition of bottom sediments on internal phosphorus load

Examples of the impact of the content of organic matter and compounds of Al and Fe in freshwater sediments on the phosphorus release from the bottom are studied. The relationships between the phosphorus release from bottom sediments and organic matter concentration in sediments of 22 lakes of the world are obtained and discussed as a result of generalization of actual data.     

Distribution and accumulation of organotin species in seawater, sediments and organisms collected from a Taiwan mariculture area

The present study was undertaken to evaluate the distribution and accumulation of tributyltin (TBT) and triphenyltin (TPhT) in seawater, sediments and selected organisms from a cage mariculture area in southern Taiwan, Hsiao Liouchiou Island. Our results show that ΣOTs were found in concentrations as high as 196 ng/L in seawater collected from the sites in Pai-Sa harbor, and up 1040 ng/g dry wt. in sediments dredged from sites within Da-Fu harbor. Also, ΣOTs concentrations of 859 ng/g dry wt. were observed in the liver of cobia (Rachycentron canadum) from mariculture cages. As most published studies have focused on the acute toxicity and bioaccumulation of organotins in mussels, the effects of organotins on cobia and other marine fauna are still poorly understood. This study highlights the significance of ΣBTs accumulation in cobia, as well as in the sediments and seawater surrounding their culture facilities.     

The enrichment characteristics of mercury in the sediments of Dongjiu and Xijiu, Taihu lake catchment, in the past century

The concentration and the enrichment factors of mercury (Hg) in the sediment cores of Dongjiu and Xijiu, Taihu Lake catchment, were studied. The accumulation fluxes, anthropogenic input concentration and anthropogenic accumulation fluxes of Hg in recent 100 years were also analyzed based on the 210Pb dating. The results indicate that the increasing concentrations of Hg in the sediments are influ-enced by natural factors and anthropogenic input simultaneously. Generally, about 2/3 of the Hg in the sediment was from anthropogenic sources. In the early 20th century, the anthropogenic input was owing to the urban development and fossil fuel consumptions surrounding the Taihu Lake and the worldwide atmospheric deposition of Hg since the industrial revolution. The concentration and an-thropogenic fluxes of Hg increased with the industrial development in the catchment since the 1930s. It reached the maximum during the middle 1970s and middle 1990s, and decreased since the middle 1990s with constraints on high pollution industries.     

Stable isotope fractionations in the evaporation of water: The wind effect

We performed pan evaporation experiments with the objective of exploring the behaviour of the long-standing Craig–Gordon (C–G) stable isotope model for evaporation under different conditions of air turbulence. The water lost through evaporation was automatically replenished so that a steady isotopic composition was reached, the value of which depended on the isotopic composition of the replenishment water and environmental parameters like temperature, relative humidity and isotopic composition of the atmospheric vapour, and the air turbulence index. The pans were exposed to artificial winds ranging from 0 to 2.5 m/s to change the air turbulence index, which governs the repartition between vapour transported by molecular diffusion and turbulent diffusion. Our data revealed that for wind speeds >0.5 m/s the isotopic composition of the evaporating water deviated from that predicted by the C–G model. This deviation was hypothetically attributed to microdroplets of liquid water removed by the wind without any isotopic fractionation. Isotope mass balance equations allowed us to quantify this water loss, which at wind speeds of ~2 m/s reached 10% of the total evaporation losses. An alternative kinetic evaporation model was proposed whereby the equilibrium layer and the atmospheric laminar layer above the evaporating water of the C–G model were destroyed by the wind and evaporated water molecules were directly injected into the atmosphere. In this model, the isotopic fractionations were due to the slower kinetics of hydrogen bond breakage between molecules in liquid water when heavy isotopes are involved. Accordingly, our data suggested that for isotope water balance studies where winds are frequently above 2 m/s, the C–G model may be inadequate without appropriate corrections for spray vaporization, or the introduction of appropriate kinetic isotope fractionation factors.