OUR和INT-ETS表征污泥活性的比较

为探寻能快速评价重金属对污泥活性影响的方法,开展了抑制污泥OUR和INT-ETS活性的试验研究.结果表明,OUR反映重金属毒性作用的灵敏性高于INT-ETS;当活性污泥受到重金属污染后,其OUR降低情况与COD的相似,而INT-ETS活性受到的抑制作用相对较小;各重金属离子表现出了不同的毒性作用,以OUR为评价参数时毒性顺序为:Hg2 ＞Cu2 ＞Ag ＞Cd2 ＞Zn2 ＞Ni2 ＞Pb2 ,以INT-ETS活性为评价参数时则为:Hg2 ＞Ag ＞Cu2 ＞Cd2 ＞Zn2 ＞Ni2 ＞Pb2 .OUR是表征污泥活性受重金属影响的较佳参数.     

Source identification of heavy metals in sewage sludge and the effect of influent characteristics: a case study from China

To advance the reclamation of sewage sludge and evaluate the potential risk during sludge application, wastewater and sludge were sampled from seven secondary wastewater treatment plants seasonally in 2016 and 2017. The influent characteristics and the accumulation of eight toxic heavy metals in sludge were analyzed. According to the results, copper, chromium, nickle and zinc were the main heavy metals constraining reclamation of sewage sludge in Shanghai and they were mainly from domestic wastewater. Influent concentration, treatment process and coexisting elements had significant effects on accumulation of heavy metals in sludge. Lead concentration in sludge from AAC plants was generally higher than that from AAO plants, but for other metals the differences were insignificant or depended on the initial concentrations. Nutrients, suspended solids and coexisting heavy metals had significant effects on heavy metal accumulation in sludge when the initial concentration was controlled.     

Pilot scale study on the ex situ electrokinetic removal of heavy metals from municipal wastewater sludges

In order to remove toxic heavy metals from municipal wastewater sludges, the ex situ electrokinetic technique was studied at pilot scale. This study focused on the feasibility of the electrokinetic removal of heavy metals from sludge and the effectiveness of this technique on the variations of abiotic (physicochemical) and biotic (intracellular and extracellular) speciations of heavy metals using several analytical methods. Even though the sludge used was taken from a municipal wastewater treatment plant, the sludge contained relatively high concentrations of target metal contaminants (Cd = 6.8 mg/kg, Cr = 115.6 mg/kg, Cu = 338.7 mg/kg, and Pb = 62.8 mg/kg). The removal efficiencies of heavy metals were significantly dependent on their speciations in the sludge matrices. The electrokinetic removal efficiencies of abiotic heavy metals exceeded 70% for the mobile and weakly bound fractions, such as, the exchangeable and carbonate fractions and were lower than 35% for the strongly bound fractions, such as, the organic/sulfide and residual fractions. In the case of the biotic heavy metals, the removal efficiencies of the extracellular fractions were slightly higher than those of the intracellular fractions.     

Effects of chromium on activated sludge and on the performance of wastewater treatment plants: A review

Chromium is a heavy metal of commercial importance, thus significant amounts are released in wastewaters. Chromium in wastewaters and in the aquatic environment is primarily encountered in oxidation stages +3 (Cr^(III)) and +6 (Cr^(VI)). Recent publications suggest that Cr^(VI) compounds are more toxic than Cr^(III) ones, while Cr^(III) has been identified as trace element, at least for complex organisms. With respect to chromium species mobility, Cr^(VI) can cross cellular membranes, which then may be oxidized to Cr^(III) and react with intracellular biomolecules. Clear conclusions cannot be derived about the critical chromium concentrations that affect activated sludge growth, as the latter is a function of a number of factors. Broadly, may be supported that activated sludge growth is stimulated at Cr^(III) concentrations up to 15 mg L⁻¹, above which is inhibited, with lethal doses lying above 160 mg Cr^(III) L⁻¹. On the other hand, literature data on Cr^(VI) effects on activated sludge are even more controversial. A number of reports support that Cr^(VI) is toxic to activated sludge at concentrations above 5 mg L⁻¹, while others report growth stimulation at concentrations up to 25 mg L⁻¹. However, all reports agree that Cr^(VI) is definitely an activated sludge growth inhibitor at higher concentrations, while 80 mg Cr^(VI) L⁻¹ have been identified as lethal dose. A number of factors have been identified to influence chromium toxicity on activated sludge, such as, pH, biomass concentration, presence of organic substances or other heavy metals, acclimation process, exposure time, etc. Naturally, the presence of chromium species in wastewaters may affect the performance of wastewater treatment plants often causing malfunctions, particularly for industrial wastewaters containing relatively high chromium concentrations. The present work reviews in a critical way the published literature on chromium effects on activated sludge, and on the operation of wastewater treatment plants.     

驯化耐盐活性污泥处理高盐度工业废水

以某石化企业废水处理厂纯氧曝气池剩余污泥为接种污泥,采用逐步提高盐度负荷的方法对活性污泥进行耐盐性驯化,考察了驯化效果.结果表明,经过较长时间的驯化,活性污泥微生物能够适应高盐度的生存环境并能在其中生长、繁殖.驯化后的活性污泥能较好地抵御高盐度冲击负荷.在进水TDS为18～35 g/L的条件下,驯化后的活性污泥纯氧曝气池对高盐度工业废水中COD的平均去除率为85.7%,比原废水处理厂常规活性污泥纯氧曝气池的高出近10%.该驯化方法可以驯化出能耐受较高盐浓度并具有良好COD降解性能的耐盐活性污泥.     

The influence of nitrilotriacetic acid on heavy metal transfer in the activated sludge process—II. At varying and shock loadings

In laboratory simulations of the activated sludge process, the impact of shock loads of the detergent builders sodium tripolyphosphate (STPP) and nitrilotriacetic acid (NTA) on the transfer of heavy metals to the effluent, has been studied. Experiments have also been undertaken in which the influent concentration of each builder was doubled, in an endeavour to simulate the effect of a “wash day”. It is apparent from the data presented that NTA, when present under either of these conditions, resulted not only in deterioration of metal removal by the activated sludge process but caused a mobilisation of heavy metals from the sludge. Copper and lead were the metals most extensively affected. The mobilisation of heavy metals from the mixed liquor to the effluent in activated sludge units acclimated to NTA, upon a doubling of the influent NTA concentration, resulted from a failure by the activated sludge unit to completely degrade the additional NTA. The concentration of NTA in the effluent rose to 4.7 mg l⁻¹ following the increase in influent concentration. Ten days were required before effluent NTA concentrations returned to values equivalent to those prior to the increase in influent concentration. When condensed phosphates were added as shock load or upon the doubling of their influent concentration only the removal of copper was adversely affected.     

Metal removal in activated sludge: the role of bacterial extracellular polymers

A combination of flocculation and settling is the mechanism by which metal removal is achieved in activated sludge. Bacterial extracellular polymers appear to play an important role in flocculation; metal cations may also be involved in this process. Extracellular polymers in activated sludge are mainly of a polysaccharide nature, although protein and nucleic acid from autolysis are constituents of the polymer matrix. Precipitated metals may be removed either by independent settling or by physical trapping in the sludge floc matrix. Metals present in the ionic form may be removed from solution by adsorption to sites on bacterial extracellular polymers. Metal ions may also be accumulated in the cytoplasm of a bacterial cell, or adsorbed on to the cell wall.If activated sludge plants are overloaded with metals, toxic effects on bacteria and other microorganisms may severely inhibit the treatment process, resulting in poor quality effluents. Acclimated bacterial cultures can tolerate much higher metal concentrations than non-acclimated cultures; these are advantageous in the treatment of metal-laden wastes.     

Long-term effects of the Aznalcóllar mine spill-heavy metal content and mobility in soils and sediments of the Guadiamar river valley (SW Spain)

In 1998, a toxic spill from a pyrite mine (Aznalcóllar, SW Spain) contaminated some 40 km2 of the Agrio and Guadiamar river valley with heavy metal-enriched tailings sludge and acidic mine water. The aim of this study is to describe the long-term effects of heavy metal migration particularly with respect to the extent of vertical redistribution of As, Cd, Cu, Fe, Pb, S, Sb and Zn in soils and sediments of the river Guadiamar 4 years after the accident. For an assessment of the mobility behaviour, chemical associations of Cu, Pb, Sb and Zn in depth profiles polluted by tailings were determined by using sequential extraction procedures. In 2002, residues of toxic tailings were found in several places along the river Guadiamar. Heavy weathering has accelerated heavy metal displacement and contamination of the surrounding soil. Two element groups of contrary mobility can be distinguished: Cd and Zn are highly mobile and show strong displacements in acidic surroundings. Accumulation zones for Cd and Zn develop in less acidic soil layers due to the occurrence of Fe oxides, which constitute retaining fractions for these elements. The immobile elements Pb and Sb represent the second group. Highest concentrations of Pb and Sb are found in the tailings sludge. Cu and As show a variable distribution pattern. As a consequence of the heavy metal migration, an accumulation zone has formed up to 30 cm into the underlying soil at the time of investigation. In the future, there may be further penetration of heavy metals to greater depths.     

Environmental aspects of the use of NTA as a detergent builder

The behaviour, fate and significance of the detergent builder nitrilotriacetic acid (NTA) has been reviewed with particular reference to the removal of NTA during wastewater treatment and the effects of NTA on heavy metal solubility both during treatment and in the receiving environment. It is concluded that NTA removal during secondary biological treatment is subject to considerable variation, both temporal and between works as a result of changes in NTA load, temperature, water hardness and treatment process parameters. As a result of such variability, effluent NTA concentrations may be sufficient to mobilise heavy metals resulting in metal contamination of receiving waters and potable waters, particularly in areas of low effluent dilution and high water re-use. Removal of NTA during primary sedimentation and septic tank treatment is concluded to be predominantly due to adsorption to the sludge solids while removal in anaerobic sludge digestion is subject to operational characteristics of the treatment works. Disposal of NTA contaminated sludge to land may contaminate groundwaters and affect heavy metal speciation, while the disposal of contaminated sludge or sewage to sea may result in toxic algal blooms, in addition to effects on metal speciation.     

Predicting metals partitioning in wastewater treatment plant influents

Interactions of heavy metals with primary sludge particulates were investigated using batch equilibrium metal uptake experiments. Results showed that metal uptake by primary sludge is significantly affected by pH. A mathematical model was developed to describe metals partitioning as a function of pH. The metal adsorption constants were determined. Results showed that for the same metal ion, the values of metal adsorption constants for primary sludge samples collected from different locations and at different times were in the same order of magnitude. Therefore, the adsorption constants were normalized and calibrated using field data. For Ag(I), Cd(II), Co(II), Cr(III), Cu(II), Ni(II), Pb(II), and Zn(II), the calibrated values of adsorption constants (logK(S)) are, respectively, 4.4, 5.1, 3.6, 4.5, 4.6, 3.6, 6.0, and 6.0. These constants can be used to predict the metal partitioning in plant influents and metal removal in primary treatment processes.     

Chemical partitioning and remobilization of heavy metals from sewage sludge dumped in Dublin Bay

During the disposal of sewage sludge to the marine environment, chemical changes may alter the mobility of trace elements, thus affecting their potential toxicity and availability to marine organisms. Primary sludge from the Ringsend treatment plant in Dublin receives both domestic waste and trade wastes which contain heavy metals, and approx. 250,000 tons per annum is periodically dumped in Dublin Bay. The purpose of this study was to determine changes which may occur in the chemical partitioning of heavy metals in the sludge during disposal. Samples of sludge were collected from the treatment plant in July 1987. Sequential chemical extraction of heavy metals (Cu, Pb, Cd, Zn, Fe, Mn) was carried out in a nitrogen-filled glove box using 1 M ammonium acetate, 1 M sodium acetate, 0.1 M hydroxylamine HCl (pH 2), 0.2 M ammonium oxalate (pH 3), 30% hydrogen peroxide and concentrated HNO₃. Seawater-extractable metal was determined by mixing subsamples of sludge with filtered seawater from Dublin Bay for 2 h. Chemical partitioning of heavy metals among solid phases in the sludge residue was redetermined by sequential chemical extraction. Both sludge and dumpsite sediments were analysed for total heavy metal content and organic content. The sludge was found to be only slightly anaerobic with a water content of 88% and significant concentrations of some metals, notably copper and zinc. Most of the non-residual copper, lead and cadmium was found in the organic/sulphidic fraction of the sludge (hydrogen peroxide extract), while the dominant phase for zinc was the moderately reducible fraction (ammonium oxalate extract) and only iron and manganese had substantial proportions of metal in more labile phases. Agitation with seawater mobilized cadmium and manganese to a significant extent (56 and 43%, respectively) but negligible amounts of copper or lead (0 and 2%, respectively). However, significant changes in solid-phase partitioning of lead and zinc occurred resulting in mobilization from stronglybound to more labile fractions. No deleterious effects were found at the dumpsite but localized effects are possibly due to the increased mobility of zinc, lead and particularly cadmium.     

Chelate-assisted phytoextraction of heavy metals in a soil contaminated with a pyritic sludge

The occurrence of many polluted areas as that affected by the accident of the Aznalcóllar pyrite mine has promoted phytoremediation as a technology able to reduce the risk of heavy metal contamination at low cost. White lupin plant has been considered a good candidate for phytoremediation. We studied the capacity of several complexing agents to improve the ability of white lupin for heavy metal phytoremediation in soils with multi-elemental pollution from acid pyritic sludge. Solution-soil interaction was studied and pot experiments with sludge-affected soil were carried out to this end. The interaction experiments indicated that EDTA and NTA were more efficient than malate and citrate in solubilizing metals (Fe, Mn, Cu, Zn, Cd), with minimum differences between EDTA and NTA. The pot trial showed that NTA was able to mobilize toxic elements from sludge-polluted soil and hence increasing their concentrations in plant (Mn, Cu, Zn, As, Cd). However, the NTA treatment promoted an increase of toxic elements concentrations, especially for As, Cd, Pb, in the lixiviates exceeding the maximum permissible levels, so a careful management of chelate is necessary.     

Toxic effect of heavy metals on the activated sludge protozoan community

The acute toxicity of five heavy metals to the protozoan community inhabiting the activated sludge of a waste treatment plant, was determined on the basis of reduction in both cell density and species richness. The activated sludge mixed-liquor was treated with different concentrations of cadmium, copper, chromium (VI), lead, and zinc for a period of 24-h. The experimental results enabled to determine the relative toxicity of the tested metals, and indicated that the order of toxicity of the five metals to the studied microbial community was generally: Cd, Cu > Pb > Zn > Cr. For nine out of sixteen protozoan species constituting the studied community was possible to determine the 24-h median lethal concentration (24-h LC₅₀) for each tested metal. Large differences appeared in sensitivities of the nine species to the metals. Ciliated protozoa such as Chilodonella uncinata and Trochilia minuta showed the highest sensitivity to all the studied metals, while Opercularia coarctata and O. minima, were the most tolerant species.     

Mass balance and distribution of sludge-borne trace elements in a silt loam soil following long-term applications of sewage sludge

Soil samples were collected at 15-cm increments to a depth of 75 cm from plots on a silt loam soil where until several years earlier and for 14 years, anaerobically digested sewage sludge had been annually applied by furrow irrigation. The study protocol consisted of four replications of 6.1 x 12.2-m plots with 0 (T0), 1/4-maximum (T1), 1/2-maximum (T2) and maximum (T3) sludge application rates randomized within blocks. When sludge applications were terminated, maximum sludge-treated plots had received 765 Mg ha-1 (dry weight equivalent) of sludge solids. Total soil concentrations of Cd, Cr, Cu, Ni, Pb and Zn had been significantly enhanced by all sludge application rates to a soil depth of 30 cm. Below the 30-cm depth, total soil Cd was increased to 75 cm, total Zn to 45 cm (T2 and T3 only), total Cr to 60 cm (T2 and T3 only), but total Cu, Pb, and Ni were not increased at depth. Despite the lack of significant increases in subsoil concentrations for some metals, mass balance calculations showed a relatively high proportion of all the above sludge-borne heavy metals to be unaccounted for in the soil profile for each application rate. Mass balance calculations of losses ranged from a high of 60% for Ni to a low of 36% for Cu and Pb. Similar losses were calculated from metal concentrations measured in soil samples taken at the time the sludge was applied. In soil surface samples (0-15 cm) from maximum sludge-treated plots, percentages of total metal concentration extracted with 4.0 M HNO3 ranged from a low of 31 for Zn to a high of 75 for Cu. Efficiency of metal extraction by HNO3 was inconsistent, depending on the soil horizon and sludge treatment, so that evaluation of HNO3-extractable metals is not a reliable method of estimating total metal retention in the profiles. In soil surface samples from maximum sludge-treated plots, the percentage of total metal contents extracted with DTPA ranged from a low of 0.03 for Cr to a high of 59 for Cd. The DTPA extractable levels of Cu, Ni, and Pb were higher in the subsoils of the sludge-treated soils, indicating that these metals had been redistributed from the surface layer to deeper zones in the profile of sludge-amended soil, despite the absence of elevated total concentrations of these three metals in the deeper subsoil.     

Heavy metal pollution of soils affected by the Guadiamar toxic flood

Total heavy metal concentrations were determined in soil samples of seven selected areas along the Guadiamar river valley affected by the toxic flood, after removal of the deposited sludge. Mean total concentrations of nine elements (As, Au, Bi, Cd, Cu, Pb, Sb, Tl and Zn) out of the 23 (As, Au, Ba, Be, Bi, Cd, Co, Cr, Cu, In, Mn, Mo, Ni, Pb, Sb, Sc, Sn, Th, Tl, U, V, Y and Zn) analysed were higher in sludge-covered soils than in unaffected soils. Mean values of total As, Au, Pb, Sb, Tl and Zn in sludge-affected soils were higher than the upper limits for normal soils world-wide. Mean concentrations of Bi, Cd and Cu were within these ranges, although some individual values exceeded the upper limits. In all sampling areas, severe heavy metal pollution was observed in the superficial layers (0-20 cm) of most of the affected soils, which decreased downward in the soil profile. Generally, in soils with more than 25% of clay, concentration of heavy metals below the 20-cm depth decreased to values close to those of the background level of the Guadiamar valley soils, while in coarser soils, heavy metal pollution penetrated below this depth, being noticeable down to a depth of at least 50-80 cm.     

Heavy metal distribution in some French forest soils: evidence for atmospheric contamination

This study is one of very few dealing with the distribution and the origin of heavy metals in French soils from a priori non-polluted forest areas. The abundance of heavy metals measured in these soils decreases as follows: Cr>Zn>Pb>Ni>Cu>Co>Cd. Total concentrations of Pb, Cr and Ni in some soils exceed the European thresholds for non-polluted soils and even the French association of normalization critical values for sludge spreading. The lowest heavy metal contents are observed in acid soils while the highest concentrations are in the calcaric cambisol and in the mollic andosol, which is rather scarce as compared with the other French forest soils. With the exception of the podzol, Cr and Ni concentrations increase with depth in all soil profiles. The distribution pattern of Co, Cu, Zn depends on the soil characteristics. In some acid soils, however, Cu and Zn decrease with depth. Pb and Cd are accumulated in the upper soil horizons. Heavy metals accumulate in deep soil horizons in relation to important clay content in the dystric planosol and stagnic luvisol. The concentration of each heavy metal is always controlled by different parameters (soil pH, iron and aluminum oxide content, clay content, organic matter and cation exchange capacity), which are heavy metal specific. This study highlights the metal-trapping character of andosol and calcaric soil, the weak heavy metal retention in acid soils, the leaching and trapping character in leached clayed soils, and the migration of heavy metals in the podzol. Pb and Cr concentrations indicate a significant enrichment in surface horizons from various soils in areas which receive significant acid atmospheric pollution. Particularly, the highest Pb content is observed in a soil located in the N-NE part of France. Lead isotope ratios measured in the cambic podzol and the calcaric cambisol, exhibit the importance of the anthropogenic sources and particularly the influence of global atmospheric inputs from leaded gasoline compared to regional and local industrial emissions. The anthropogenic Pb contribution is estimated to 83, 30 and 11%, respectively, for surface, intermediate and deep horizons of the cambic podzol located in the northern part of France, and to 68% in surface horizon of the calcaric cambisol located in the Alps.     

Accumulation of heavy metals in sunflower and sorghum plants affected by the Guadiamar spill

The collapse of a pyrite-mining, tailing dam on 25 April 1998 contaminated approximately 2000 ha of croplands along the Agrio and Guadiamar river valleys in southern Spain. This paper reports the accumulation of chemical elements in soil and in two crops--sunflower and sorghum--affected by the spill. Total concentrations of As, Bi, Cd, Cu, Mn, Pb, Sb, Tl and Zn in spill-affected soils were greater than in adjacent, unaffected soils. Leaves of spill-affected crop plants had higher nutrient (K, Ca and Mg for sunflower and N and K for sorghum) concentrations than controls, indicating a 'fertilising' effect caused by the sludge. Seeds of spill-affected sunflower plants did accumulate more As, Cd, Cu and Zn than controls, but values were below toxic levels. Leaves of sorghum plants accumulated more As, Bi, Cd, Mn, Pb, Tl and Zn than controls, but these values were also below toxic levels for livestock consumption. In general, none of the heavy metals studied in both crops reached either phytotoxic or toxic levels for humans or livestock. Nevertheless, a continuous monitoring of heavy metal accumulation in soil and plants must be established in the spill-affected area.     

堆肥处理对排水污泥中重金属的钝化作用

讨论了城市排水污泥中重金属的含量和形态分布特征，分析了堆肥处理对污泥中重金属结合形态转化的影响。根据不同学者的研究结果，提出堆肥处理可降低污泥中Zn、Cu、Pb、Mn等重金属的活性，并指出堆肥处理是降低污泥在土地利用中重金属污染风险的途径。     

改性凝胶球包埋活性污泥对污水中重金属的响应

采用改性凝胶球包埋活性污泥,并将其用作毒性预警中的优化生物载体,结合水相指标和微生物活性指标,综合分析重金属对水质和凝胶球包埋活性污泥的影响。结果表明,经聚氧化丙烯三醇(PPT)改性的凝胶球具有较大的比表面积和较小的孔径。当进水中存在Zn²⁺、Cd²⁺和Cr⁶⁺时,水相指标pH值、电导率和氧化还原电位(ORP)均存在明显的变化;比耗氧速率(SOUR)、氨氧化速率(AUR)和污泥电子传递体系(ETS)活性等微生物活性指标也与重金属种类和浓度相关;微量重金属有助于提高微生物活性,但高浓度重金属则会抑制微生物活性。Zn²⁺、Cd²⁺和Cr⁶⁺对ETS活性的半抑制浓度分别为8. 71、44. 11和19. 94 mg/L。     

腐殖土活性污泥中重金属的浸出行为研究

在不同pH值和腐殖土投加量条件下,对活性污泥中Zn、Ni、Cu和Pb四种重金属的浸出行为进行了研究。结果表明,污泥中Zn和Ni的浸出率随pH值的降低而呈明显升高的趋势,Cu和Pb的浸出率也随pH值的降低而升高,但变化幅度相对较小。在酸性条件下,随着腐殖土投量的增加,活性污泥中Zn、Ni、Cu和Pb的浸出率明显降低;而在中性偏碱性条件下,这种变化趋势不明显。投加腐殖土能明显改变活性污泥中重金属的形态分布,促进重金属的稳定化,进而显著改善重金属的浸出行为。