Effects of long-term irrigation with treated wastewater. Part I: Evolution of soil physico-chemical properties

The long-term impact of irrigation on a Mediterranean sandy soil irrigated with Treated wastewater (TWW) since 1980 was evaluated. The main soil properties (CEC, pH, size distribution, exchangeable cations and chloride, hydraulic conductivity) as well as the organic matter and Cu, Cr and Pb speciation in an irrigated soil and a non-irrigated control soil at various soil depths were monitored and compared during a 2 years experiment. In this first part, the evolution of the physico-chemical soil properties was described. The irrigation with TWW was beneficial with regard to water and nutrient supplying. All the exchangeable cations other than K⁺ were higher in the irrigated soil than in the reference one. A part of the exchangeable cations was not fixed on the exchange complex but stored as labile salts or in concentrated soil solution. Despite the very sandy soil texture, both saturated and unsaturated hydraulic conductivity exhibited a significant diminution in the irrigated soil, but remained high enough to allow water percolation during rainy periods and subsequent leaching of accumulated salts, preventing soil salinization. In the irrigated soil, exchangeable sodium percentage (ESP) exhibited high values (20% on average) and the soil organic C was lower than in the reference. No significant effect was noticed on soil mineralogical composition due to irrigation.     

Adsorptive removal of Cu(II) and Pb(II) onto mixed-waste activated carbon: kinetic,thermodynamic, and competitive studies and application to real wastewater samples

This work aimed to investigate the adsorption characteristics, both kinetically and thermodynamically, of Cu(II) and Pb(II) removal from aqueous solutions onto mixed-waste activated carbon, as well as to study the competitive behavior found in mixed heavy metal solution systems. This study shows that activated carbon prepared from mixed waste is an effective adsorbent for the removal of Cu(II) and Pb(II) from aqueous solutions, with the aim of detoxifying industrial effluents before their safe disposal onto water surfaces. The adsorption process was characterized in terms of kinetic and thermodynamic studies. In addition, the influence of presence of Cu(II) and Pb(II) in a competitive system was investigated. The results showed that the maximum adsorption capacities were gained at a pH of 6 with a contact time of 180 min, a metal solution concentration of 300 ppm, and an adsorbent dose of 0.3 g/L. The adsorption process was found to follow a pseudo-first-order kinetic model. Thermodynamic parameters such as ΔG ^o, ΔH ^o, and ΔS ^o showed that the sorption process was spontaneous and endothermic in nature. A competitive study demonstrated the applicability of mixed-waste activated carbon to adsorb Cu(II) and Pb(II) from a solution of mixed metals. In addition, the adsorption capacity was found to be as effective as other adsorbents reported in the literature. The developed adsorptive removal procedure was applied for treatment of real wastewater samples and showed high removal efficiency.     

Biosorption of Pb, Cd, Cu and Zn from the wastewater by treated Azolla filiculoides with H2O2/MgCl2

The adsorption of heavy metals onto treated Azolla filiculoides by H₂O₂/MgCl₂, as a cosmopolitan free-floating waterfern, was investigated from aqueous solutions in the batch biosorption experiments. The maximum uptake capacities of the collected Azolla from rice field at the optimal conditions for Pb, Cd, Cu and Zn ions were approximately 228, 86, 62 and 48 mg/g (dry Azolla), respectively. On the other hand, the maximum uptake capacities of the collected Azolla from the Anzali International Wetland in the north part of Iran at the same conditions for these heavy metals were about 124, 58, 33 and 34 mg/g (dry Azolla), respectively. Such decrease of uptakes is due to the pollution of Anzali International Wetland, which reduces the capacity uptake of metals. The recovery of biosorbed heavy metals from the rice field Azolla was carried out by HCl and NaCl desorbents that the recovery of 64–86% and 51–72% was occurred, respectively.     

ICP-MS测定土壤中的As、Cr、Pb、Se、Cu和Zn

本文用电感耦合等离子质谱法(ICP-MS)测定了土壤的As、Cr、Pb、Se、Cu和Zn6种微量元素的质量分数,以In作为内标进行基体效应的补偿,方法快速灵敏,回收率为92.4%～106.8%,相对标准偏差小于5.0%,结果达到国家标准要求。     

The effect of long-term soil irrigation by wastewater on organic matter, polycyclic aromatic hydrocarbons, and heavy metals evolution: case study of Zaouit Sousse (Tunisia)

Irrigation by treated wastewater (TWW) can pollute the soil by different organic and inorganic compounds. The pollution level can depend on the irrigation period, soil nature, and wastewater characteristics. Since 1989, the Zaouit Sousse area (central Tunisian) has been irrigated by treated wastewater. The irrigation period and the mineralogy of soil composition change from one locality to another in Zaouit Sousse area. In this work, we are interested in organic compounds, polycyclic aromatic hydrocarbons (PAHs), and heavy metals (HMs) evolution. One control soil (S1) and four irrigated areas soil (S2, S3, S4, and S5) were chosen. The soil samples differ by the irrigation period and soil characteristics. Total PAHs content in control soil was 66.2 ng?g^?1 and in irrigated areas were between 46.23 and 129.51 ng?g^?1. The PAHs content in irrigated soil, except S5 which has been irrigated with wastewater for 20 years and contains the highest clay fraction percent, decreased with the irrigation period (from 0 to 20 years). The microbial degradation may decrease the PAHs concentrations in the soil thanks to bacterium brought by TWW and the important soil permeability. Concentration of heavy metals ranged from 24 to 1,320 μg?L^?1. The HMs (Cu, Cr, Zn, Fe, Ni, Pb, and Cd) contents decreased with the irrigation period (from 10 to 20 years). So, following the PAHs aerobic bio-degradation, this organic compound discharges their absorbed heavy metals which leached to deeper levels. The Cr, Cu, Al, Zn, and Cd mobility depend on the clay yield too. However, the PAHs and Pb mobility are also related to humic substance quantities. Cr and Cu have affinities both to clay and humic substance quantities.     

Effects of weathering on organic matter: Part II: Fossil wood weathering and implications for organic geochemical and petrographic studies

Bulk geochemical, petrographical, mineralogical and molecular compositions of unweathered, weathered and transitional zones of a Middle Jurassic fossil wood were analyzed to trace changes caused by oxidative weathering of the immature terrestrial organic matter (OM). The occurrence of such zones was confirmed by the mineral composition, showing replacement of siderite and pyrite by goethite. Vitrinite reflectance analysis of weathered and unweathered fossil wood samples revealed that weathering elevated the vitrinite reflectance values by ca. 0.1%, which should be taken into account during modeling of low maturity terrestrial OM. In the weathered part of the wood, most of the biomarkers and biomolecules were totally removed or the concentration decreased significantly. The concentration of most of the polynuclear aromatic hydrocarbons (PAHs) decreased by 50–80%, being >90% for the more reactive and less stable benzo[a]pyrene and perylene. On the other hand, several aromatic compounds, like phenanthrene and its methyl derivatives, phenyl naphthalenes, fluoranthene and oxygen-containing aromatic compounds increased in concentration in the weathered zone. This results from processes such as formation of phenyl derivatives of PAHs and their cyclization, as well as aromatization of diterpenoids and incorporation of oxygen into aromatic structures. Weathering should always be considered in studies of fossilized terrestrial OM, especially in the case of thermal maturation modeling, because it significantly decreases the OM content and total sulfur content, changes vitrinite reflectance values and alters the extract composition as a result of organic compound degradation.     

Structural and vibrational behaviour of fluorapatite with pressure. Part II: in situ micro-Raman spectroscopic investigation

 High-pressure Raman investigations were carried out on a synthetic fluorapatite up to about 7 GPa to analyse the behaviour of the phosphate group's internal modes and of its lattice modes. The Raman frequencies of all modes increased with pressure and a trend toward reduced splitting was observed for the PO₄-stretching modes [(ν_3a(A_g) and ν_3b(A_g); ν_3a(E_2g) and ν_3b(E_2g)] and the PO₄ out-of-plane bending modes [ν_4a(A_g) and ν_4b(A_g)]. The pressure coefficients of phosphate modes ranged from 0.0047 to 0.0052 GPa⁻¹ for ν₃, from 0.0025 to 0.0044 GPa⁻¹ for ν₄, from 0.0056 to 0.0086 GPa⁻¹ for ν₂ and 0.0046 for ν₁ GPa⁻¹, while the pressure coefficients of lattice modes ranged from 0.0106 to 0.0278 GPa⁻¹. The corresponding Grüneisen parameters varied from 0.437 to 0.474, 0.428, 0.232 to 0.409 and 0.521 to 0.800 for phosphate modes ν₃, ν₁, ν₄, ν₂, respectively, and from 0.99 to 2.59 for lattice modes. The vibrational behaviour was interpreted in view of the high-pressure structural refinement performed on the same crystal under the same experimental conditions. The reduced splitting may thus be linked to the reduced distortion of the environment around the phosphate tetrahedron rather than to the decrease of the tetrahedral distortion itself. Moreover, the amount of calcium polyhedral compression, which is about three times the compression of phosphate tetrahedra, may explain the different Grüneisen parameters. Received: 25 April 2000 / Accepted: 20 December 2000     

Bioaccumulation of Cu, Zn and Ni from the wastewater by treated Nasturtium officinale

Aquatic plants are well known in accumulating and in concentrating heavy metals. In this study, several physiological responses of aquatic vascular plant, Nasturtium officinale (watercress), which were elevated concentrations of copper, zinc and nickel have been investigated. It was found that Nasturtium officinale were able to accumulate both copper and zinc at upper levels, but was able to accumulate to nickel at low levels. The final goal of this work was to examine the copper, zinc and nickel uptake using this aquatic plant from their solutions.     

Influence of operating conditions on the removal of Cu, Zn, Cd and Pb ions from wastewater by adsorption

Nile Rose Plant was used to study adsorption of several cations (Cu²+, Zn²+, Cd²+ and Pb²+) from wastewater within various experimental conditions. The dried leaves of Nile Rose Plant were used at different adsorbent/ metal ion ratios. The influence of pH, contact time, metal concentration, and adsorbent loading weight on the removal process was investigated. Batch adsorption studies were carried out at room temperature. The adsorption efficiencies were found to be pH dependent, increasing by increasing the pH in the range from 2.5 to 8.5 exept for Pb. The equilibrium time was attained within 60 to 90 min. and the maximum removal percentage was achieved at an adsorbent loading weight of 1.5 g/50 mL mixed ions solution. Isothermal studies showed that the data were best fitted to the Temkin isotherm model. The removal order was found to be Pb²⁺> Zn²⁺> Cu²⁺> Cd²⁺. The surface IR-characterization of Nile rose plant showed the presence of many functional groups capable of binding to the metal cations.     

Sorption of PAR–metal complexes on activated carbon as a rapid preconcentration method for the determination of Cu, Co, Cd, Cr, Ni, Pb and V in ground water

A simple, rapid and field-oriented preconcentration method is described for the determination of Cu, Co, Cd, Cr, Ni, Pb and V in ground water samples by flame AAS. The method is based on sorption of trace elements as metal-pyridyl azo resorcinol (M-PAR) complexes on activated carbon (AC) at pH 5.5±0.5. The effects of various parameters for quantitative sorption of M-PAR chelates on AC are discussed. The trace elements are desorbed from AC simply by treating AC with 1.6 M nitric acid, thus avoiding the tedious and time consuming operation of ashing AC. An enrichment factor of 200 or greater is easily achievable. The trace elements could be determined down to 1 ppb (V at 5 ppb) with ±15% relative error. The RSD of the method is ±15% at the practical determination limit of 1 ppb with an enrichment factor of 200. The major advantage of the method is the possibility of performing the preconcentration at the sampling site and hence a small preconcentrated volume could be sent for instrumental analysis, thus preventing sorption on a container during storage. The method has been applied to numerous ground water samples for the determination of these trace analytes at ppb levels in connection with the hydrogeochemical exploration for uranium.     

Trace metal behaviour in riverine sediments: Role of organic matter and sulfides

Three sediment cores were collected in the Scheldt, Lys and Spiere canals, which drain a highly populated and industrialized area in Western Europe. The speciation and the distribution of trace metals in pore waters and sediment particles were assessed through a combination of computational and experimental techniques. The concentrations of dissolved major and trace elements (anions, cations, sulfides, dissolved organic C, Cd, Co, Fe, Mn, Ni, Pb and Zn) were used to calculate the thermodynamic equilibrium speciation in pore waters and to evaluate the saturation of minerals (Visual Minteq software). A sequential extraction procedure was applied on anoxic sediment particles in order to assess the main host phases of trace elements. Manganese was the most labile metal in pore waters and was mainly associated with carbonates in particles. In contrast, a weak affinity of Cd, Co, Ni, Pb and Zn with carbonates was established because: (1) a systematic under-saturation was noticed in pore waters and (2) less than 10% of these elements were extracted in the exchangeable and carbonate sedimentary fraction. In the studied anoxic sediments, the mobility and the lability of trace metals, apart from Mn, seemed to be controlled through the competition between sulfidic and organic ligands. In particular, the necessity of taking into account organic matter in the modelling of thermodynamic equilibrium was demonstrated for Cd, Ni, Zn and Pb, the latter element exhibiting the strongest affinity with humic substances. Consequently, dissolved organic matter could favour the stabilization of trace metals in the liquid phase. Conversely, sulfide minerals played a key role in the scavenging of trace metals in sediment particles. Finally, similar trace metal lability rankings were obtained for the liquid and solid phases.     

The long-term fate of Cu, Zn, and Pb adsorption complexes at the calcite surface: An X-ray absorption spectroscopy study

In this study, the speciation of Zn²⁺, Pb²⁺, and Cu²⁺ ions sorbed at the calcite surface was monitored during a 2.5-year reaction period, using extended X-ray absorption spectroscopy to characterize metal speciation on the molecular scale. Experiments were performed using pre-equilibrated calcite-water suspensions of pH 8.3, at metal concentrations below the solubility of metal hydroxide and carbonate precipitates, and at constant metal surface loadings. The EXAFS results indicate that all three metals remained coordinated at the calcite surface as inner-sphere adsorption complexes during the 2.5-year ageing period, with no evidence to suggest slow formation of dilute metal-calcite solid solutions under the reaction conditions employed. All three divalent metals were found to form non-octahedral complexes upon coordination to the calcite surface, with Zn²⁺ adsorbing as a tetrahedral complex, Cu²⁺ as a Jahn-Teller distorted octahedral complex, and Pb²⁺ coordinating as a trigonal- or square-pyramidal surface complex. The non-octahedral configurations of these surface complexes may have hindered metal transfer from the calcite surface into the bulk, where Ca²⁺ is in octahedral coordination with respect to first-shell O. The use of pre-equilibrated calcite suspensions, with no net calcite dissolution or precipitation, likely prevented metal incorporation into the lattice as a result of surface recrystallization. The results from this study imply that ageing alone does not increase the stability of Zn²⁺, Pb²⁺, and Cu²⁺ partitioning to calcite if equilibrium with the solution is maintained during reaction; under these conditions, these metals are likely to remain available for exchange even after extended sorption times.     

高压微波消解法测定醋酸纤维过滤器采集的微尘粒子中的砷镉钴铬铜铁锰镍铅钒锌

最新的流行病学研究表明,空气中较高浓度的悬浮细颗粒可能对人类的健康有不利的影响。根据该项研究显示,由于心脏病、慢性呼吸问题和肺功能指标恶化而导致死亡率的升高与细尘粒子有关。这些研究结果已经促使欧盟于1999年4月出台了限制空气中二氧化硫、二氧化氮、氧化氮、铅和颗粒物含量的法案（1999/30/EC）,对各项指标包括对可吸入PM10颗粒的浓度提出了新的限制性指标。PM10颗粒是指可以通过预分级器分离采集的气体动力学直径小于10 μm的细颗粒。目前研究的兴趣重点逐步偏向PM2.5这些更细微颗粒物,PM2.5这种颗粒物对健康有明显的不利影响。在欧盟指令2008/50/EC中,对PM10和PM2.5都提出了具体测定要求。     

A decade of change in the Skidaway River estuary II. Particulate organic carbon, nitrogen, and chlorophylla

A sampling program was initiated in 1986 in the Skidaway River estuary, a tidally dominated subtropical estuary in the southeastern USA. Hydrography, nutrients, particulate organic matter (POM), and microbial and plankton abundance and composition were measured at weekly intervals at high and low tide on the same day at a single site. Hydrographic and nutrient data during 1986–1996 were given in Verity (2002); particulate organic carbon (POC), nitrogen (PON) and chlorophylla (chla) are presented here; plankton data will be presented elsewhere. Chla was fractionated into <8 μm and >8 μm size classes. All classes of POM exhibited distinct seasonal patterns superimposed upon significant long-term increases during the study period. Total chla, <8 μm chla, and >8 μm chla increased 36%, 61%, and 18%, respectively, however the fraction of total biomass attributable to small phytoplankton (<8 μm) increased 25%. The annual amplitude between minimum and maximum stock sizes increased significantly, meaning that bloom events became larger. POC and PON also increased 16% over the decade and, as observed with patterns in chla, exhibited increases in annual amplitude. The C:N ratio was typically 6.4–6.6 (wt:wt) and did not change significantly, while the annual mean C:Chla ratio decreased 19% from 165 to 140. These characteristics indicated highly labile POM composed of significant amounts of detritus, but which became increasingly autotrophic with time. Averaged over the decade, temperature explained 45–50% of the variance in POM. Nutrients were even better predictors of POM, as 60–75% of the variance in chla, POC, and PON were explained by ambient concentrations of DIN, or PO₄. Combined with significant increases in NO₃, NH₄, PO₄, Si(OH)₄, and DON during 1986–1996, these data strongly suggest that anthropogenic activities contributed to increased loading of dissolved nutrients, which became incorporated into living and nonliving particulate organic matter.     

Hydrothermal growth of OH-phlogopite single crystals II. Role of Cr and Ti adsorption on crystal growth rates

OH-phlogopite mica overgrowths on natural seeds have been obtained at P_sol=1 kbar and 522–535°C growth temperatures by means of the thermal gradient method of hydrothermal growth. Solutions used were KOH (6.5 m)-H₂O with Cr or Ti introduced as additives. The growth kinetics of the lateral single faces of the mica have been measured as a function of the nominal relative supersaturation applied and then compared to similar measurements formerly made from Cr- and Ti-free hydrothermal solutions. It is shown that Cr stimulates a sharp transition of growth mechanisms from spiral growth to two-dimensional nucleation or one-dimensional roughening for all lateral faces as the supersaturation increases. On the other hand, Ti causes the latter two possible growth mechanisms to predominate over the entire investigated supersaturation range (3.4–10.2%). Cr as well as Ti additives decrease the growth kinetics of all lateral faces. This is indicative of a growth retardation effect due to adsorption. Furthermore, Cr and Ti act as growth habit modifiers, i.e. they adsorb differently onto the two groups of lateral forms: {11l}, {02l} and {13l}, {20l}. Ti and Cr stabilize both a pseudohexagonal habit, bounded by {11l} + {02l} for Ti, but by {13l} + {20l} for Cr. Chemical sector-zoning takes place for Cr and Ti among lateral forms. Both incorporate more in the {13l} and {20l} sectors than they do in the {11l} and {02l} ones, with a much stronger concentration contrast for Ti. The incorporation of both transition elements appears as poorly sensitive to the growth kinetics of the faces but more likely controlled by crystal-solution interface phenomena.     

无高氯酸常压酸溶-ICP-MS法同时测定土壤中的As、Cd、Pb、Cr、Zn、Cu、Ni

采用无高氯酸常压酸溶分解土壤样品,利用等离子体质谱法可以1次溶矿测定As、Cd、Pb、Cr、Zn、Cu、Ni 7个重金属元素,具有较高的分析效率、较好的分析质量、较低的分析成本。实验表明,试样溶液中氯的含量对分析元素信号有较大影响。采用硝酸-氢氟酸-硫酸-过氧化氢分解样品以避免引入氯离子,从而能有效避免Cr、As元素在样品分解过程中的损失和氯离子产生的质谱干扰。Cd的测定需采用干扰校正公式扣除Sn的干扰。对于As元素,若试样溶液中不含或仅含微量的氯离子,采用标准模式测定即可得到理想的分析结果,否则必须采用CCT模式进行测定。除As以外的其他元素不论在标准模式或CCT模式下均能得到理想的分析结果。     

Conservative behaviour of riverine dissolved organic carbon in the Severn Estuary: chemical and geochemical implications

The distribution, variability and chemical behaviour of dissolved organic carbon (DOC) was investigated over 2$\text{1}\text{2}$ years in the Severn Estuary and Bristol Channel, UK. The concentrations of riverine DOC (3.1–7.8 mg C l^?1) covaried with river flow and were invariably conservative in this turbid slowly flushing (~200 days) estuary, indicating that any microbial degradation, chemical flocculation or adsorption processes do not affect the flux of riverine DOC through the estuary. The DOC inputs from the Severn (1.7–2.7 × 10¹⁰ g Cyr^?1) and other rivers (2.6–3.4 × 10¹⁰ g Cyr^?1) are the principal sources of DOC in the estuary and correspond to an export of 0.7–1.1% of the terrestrial productivity from the river catchment to the ocean. This export rate is in accord with recent predictions derived from global compilations of organic inputs from rivers and would imply that the global flux of riverine DOC could be as high as 7.8 × 10¹⁴ g Cyr^?1 which is 5 times greater than some previous estimates.The geochemical significance of a conservative delivery of riverine DOC to the ocean is that irrespective of which flux estimate is considered, such river inputs would make a significant contribution (~SO%) to oceanic DOC, and that the steady-state oceanic DOC flux would have to be significantly greater than present estimates (2.9 × 10¹⁴ g Cyr^?1) which are based on a mean radio carbon age of 3400 yr.An alternative, more realistic DOC flux model, which assumes a polydisperse age distribution about the mean age, is shown to yield the higher oceanic DOC fluxes required. Flocculation and adsorption processes would remove less than 10% and 0.2% respectively of riverine DOC in estuaries.     

北京城区土壤中Hg、Pb、Cd、Cu及Zn化学形态及环境效应

为弄清北京城区土壤中Hg、Pb、Cd、Cu及Zn五种重金属元素的化学形态分布特征,系统采集了126件城区表层土壤样品,采用连续提取法对重金属元素各化学形态含量进行了测定。结果表明:土壤中土壤中Hg、Pb、Cd、Cu、Zn含量差异显著。Hg元素以残渣态和强有机结合态为主,Cd元素离子交换态、碳酸盐结合态、残渣态、铁锰氧化物结合态含量较高,Pb、Cu、Zn元素以残渣态、铁锰氧化物结合态为主。Hg元素的有效态含量最低(不足1%),现情况下不会对环境造成污染;Cd元素的有效态含量最高(40%),生物有效性和潜在生态危害性较大,运用植物修复技术对其治理为经济有效的方法;Pb、Cu、Zn有效态含量较低(约10%),生物有效性和潜在生态危害性均有限。各元素形态与全量之间相关程度虽有差别,但基本呈正相关关系。