污泥与煤、木屑燃烧过程中重金属排放特性研究

为了考察燃料燃烧过程中重金属的迁移转化规律，对污泥、煤与木屑及其混合物在不同温度下氧气中燃烧灰渣中的重金属元素进行分析。结果表明，燃料中重金属在高温燃烧时表现出不同的挥发特性，大部分元素随着温度的升高挥发率增加，其中Cd、Pb和Zn元素挥发性较强，Cr、Cu和Ni挥发性较弱。污泥与木屑混合燃烧灰渣仍以污泥灰为主，重金属含量与污泥灰相近，污泥中混入煤后使灰中大部分重金属含量有所降低。燃烧过程会改变重金属存在形态，污泥与煤原料中以酸溶态和可还原态存在的重金属含量较高，具有较强的生物有效性和迁移性，而燃烧灰渣中酸溶态和可还原态含量显著下降，混合燃烧灰渣中除As外的其他重金属几乎全部以残渣态存在，其含量达到90％以上，焚烧过程有效降低了燃料灰渣中重金属的生物毒性。     

高温堆肥与蚯蚓堆肥对城市污泥重金属形态的影响

采用高温堆肥和蚯蚓堆肥工艺，研究了城市污泥与锯末、粉煤灰或磷矿粉按不同比例混合堆肥前后重金属（Cu、Pb、Zn、Cd和As）交换态、碳酸盐结合态、铁锰氧化物结合态、有机结合态和残留态的变化。研究表明：高温堆肥和蚯蚓堆肥前后各试验污泥的重金属形态和含量呈现出不同的变化，都可以降低污泥中交换态Cu、Pb、Zn、Cd和As的含量；对于Cu和Pb，高温堆肥优于蚯蚓堆肥；对于Zn、Cd和As，蚯蚓堆肥优于高温堆肥。2种堆肥方式中，粉煤灰用量为10%的钝化效果优于20%，磷矿粉的钝化效果同粉煤灰一样。     

生物沥滤去除污泥、土壤和底泥中3种重金属比较研究

以硫酸亚铁为底物,对城市污泥、土壤和河流底泥进行生物沥滤实验,探讨了污泥、底泥和土壤在沥滤过程中重金属的去除效果和化学形态转化规律,了解当地土壤在酸化条件下重金属的释放过程,并对三者的研究结果进行比较分析。结果表明,污泥生物沥滤对重金属(Zn、Cu和Pb)的沥滤的沥滤效果较佳(去除率75.45%、63.12%和40.96%)。沥滤过程中,重金属Cu在生物沥滤中期(3~5 d)沥出效果较好,而Zn和Pb则在沥滤后期(5~9 d)。同一重金属在不同沥滤体系中的形态变化过程差异较大,沥滤后的污泥、土壤和底泥中的重金属大部分呈现稳定状态。     

不同焚烧温度下开发区污泥焚烧渣分析

在不同焚烧温度条件下采用可控温管式炉焚烧开发区干污泥,对污泥焚烧渣中微观形貌、元素分布、矿物组成以及重金属总量及其形态进行了分析研究。实验结果表明,污泥焚烧渣在焚烧温度为900℃出现明显的结焦现象,在焚烧温度为1 100℃时焚烧渣结焦的微观表面致密。XRD分析发现温度的升高使污泥烧渣中出现NaA lS iO4等性质相当稳定的物质。不同重金属在底渣中的总量分布及其形态特征受焚烧温度的影响程度不同。焚烧温度的提高使污泥中重金属的残渣态比例增高,使污泥焚烧对环境的影响减小。     

基于生物淋滤的城市污泥重金属溶出及形态迁移

利用生物淋滤法处理城市污泥,以生物淋滤过程中pH、ORP(氧化还原电位)变化以及重金属(Zn、Cu、Cd)溶出率为指标,考察淋滤菌接种比例、初始pH、淋滤时间对生物淋滤的影响,并分析了生物淋滤前后,重金属形态变化以及重金属的生物有效性和迁移性。结果表明富集筛选的嗜酸性氧化亚铁硫杆菌(A.f)可有效溶出污泥中的重金属。生物淋滤最佳条件为:初始pH=4.00,淋滤菌接种比例30%,重金属Zn,Cu,Cd在第10天的整体处理效果最优,溶出率分别达到75.30%、50.40%和74.44%。BCR形态分析表明:原污泥中Zn,Cu,Cd主要以弱酸提取态、可还原态和氧化态存在,残渣态较少;生物淋滤之后,3种重金属弱酸提取态、可还原态和氧化态含量有不同程度降低,其中,可还原态含量降低最为显著,残渣态基本无变化,并且淋滤后污泥中重金属氧化态及残渣态所占比例较淋滤前高,污泥稳定性得到提升。生物淋滤可以通过减少污泥中重金属含量和改变重金属形态降低其生物有效性和迁移性。     

污泥微波热解过程重金属转化特性与风险评估

利用微波反应器在500~900℃的目标温度下,高温热解干污泥与Si C混合物(质量比为2.5∶1)以制取不同污泥焦,选取改进欧盟BCR逐级提取法对微波热解前后污泥焦中重金属(Cr、Cu、Pb、Ni)形态变化进行分析。同时对微波污泥热解焦进行RAC风险评估,探寻微波热解固定效能与污泥焦使用安全性与可行性。结果表明,随着微波热解温度的升高,重金属中残渣态(F4)大幅增加稳定性显著改善,与原样相比,Cr与Pb的可氧化态(F3)明显减少,分别由原样中73.86%和51.96%下降至5.98%和4.47%,Cu的可氧化态(F3)在500℃以上变化不明显。此外,微波热解焦中Ni的风险系数显著降低,其RAC形态风险系数由33.23骤降至0.78,其他3种重金属的风险系数也有不同程度的降低。     

Fenton氧化剩余污泥过程重金属迁移及其形态变化

采用Fenton氧化处理含重金属剩余污泥,通过BCR法测定并分析了污泥处理过程各重金属形态的变化,重点考察了pH、H_2O_2投加量、H_2O_2/Fe~(2+)比、温度(T)和反应时间(t)5个因素对重金属迁移及形态变化的影响。结果表明,利用Fenton氧化处理剩余污泥,污泥重金属形态变化显著,且受到初始pH、H_2O_2投加量、H_2O_2/Fe~(2+)比和温度的影响,但反应时间的影响较小。正交实验结果显示,Fenton氧化处理污泥的最佳条件为:初始pH1、H_2O_2投加量12 g·L~(-1)、H_2O_2/Fe~(2+)比10和温度50℃,此时污泥Cu、Mn和Zn 3种重金属的弱酸溶解态含量达到最高值,分别为72.66%、90.12%和87.51%。在最佳条件时,污泥上清液中Cu、Mn和Zn含量可分别从0.08、0.263和0.01 mg·L~(-1)增加到15.08、17.49、32.74 mg·L~(-1)。研究表明,Fenton氧化污泥过程提高了污泥中弱酸溶解态重金属含量,利于重金属从固相向液相转移,从而有效降低污泥饼中重金属含量,有利于污泥脱水后的进一步处理及其资源化。     

石灰污泥共热法在水泥煅烧中的应用

利用水泥窑尾的高温废气干化污泥是处理污泥且节约能源的新方法。为了模拟窑尾废气干化污泥的生产工艺,试验对污泥与石灰共热干化,研究了石灰(CaO)在污泥热干化过程中作用,可提高污泥的干化速率,减少有害气体排放及提高干化污泥的稳定性。研究表明,当石灰掺量质量百分含量达到10%时,250℃下污泥干化速率同比提高了19.6%;释放的H2S气体减少了95.1%;污泥中有机物含量减少了77.87%。     

城市污泥微波干化工艺及干化特性研究

采用微波和烘箱结合及全程烘箱2种方式对城市污泥干化进行对比研究,考察了不同粒径、微波干化预处理、预处理时间及烘箱温度对污泥干燥特性的影响。结果表明,同一温度条件下,微波预处理时间越长,污泥干化速率越快。最优条件下,全程烘箱污泥达到最大干化速率的含水率为77%。微波干燥污泥具有时间短、干燥速率大的特点,微波和烘箱结合对比全程烘箱干化速率高且能耗低。     

石灰干化污泥对土壤重金属稳定化处理的效果

以采自湖南省嘉禾县重金属复合污染土壤为研究对象,采用城市污水处理石灰干化污泥作为稳定剂,对污染土壤进行稳定化处理,并采用TCLP和BCR连续提取法对稳定化效果进行分析和评价。研究结果表明,单独使用石灰干化污泥,TCLP浸出浓度随着干化污泥质量分数的增加而显著减少,干化污泥的质量分数为40%时,稳定化率最大为Zn-98.92%、Cd-99.06%、Pb-96.84%;但是干化污泥的高pH值导致稳定后土壤中As的浸出增加。为了恢复植物生长功能,经过亚铁盐和磷酸调节pH后,石灰干化污泥稳定过的土壤pH有效降低,同时亚铁盐和磷酸有利于促进Pb和Zn的稳定效果;但是对Cd的稳定有负面影响;另外,亚铁盐的加入同时可以减少As的浸出浓度。经处理后土壤中重金属形态由不稳定态转为稳定态,使重金属的浸出浓度明显降低,减少了土壤重金属的浸出毒性。该研究结果表明,石灰干化污泥可以作为资源回收利用,应用于重金属污染土壤的修复中,并能改善稳定后土壤适宜植物生长的理化性质。     

Emission inventory of eight elements,Fe, Al,K, Mg,Mn, Na,Ca and Ti,in dust source region of East Asia

Based on calculation of the emission rate of the atmospheric mineral dust and the data of elemental contents in surface soils, this paper calculates the emission inventory of eight main elements of the atmospheric dust, Fe, Al, K, Mg, Mn, Na, Ca and Ti, in the dust source region of East Asia. As the dust sources in both Northern China and the Southern Mongolia are of three types and, in each of the six source type areas, surface soils are relatively uniform in soil types and soil texture, a simple method to calculate the emission of an element in one source type area is proposed by multiplying the total emission of the dust PM₁₀ and PM₅₀ in the source type area with the mean percentage content of the element in surface soils of the area. Comparison of our calculation of the total Fe emission in the source region of East Asia with the total Fe deposition to the North Pacific Ocean, measured and calculated by previous authors, shows very good agreement. This general method can also be used for the emission calculation of any other element.     

Effects of Ni, Cr, Hg, Cu, Zn, Al on the dissolved oxygen balance of streams

Inorganic metals besides their direct toxic effects, carry the potential of causing serious variations on existing ecosystems in receiving waters. Self purification mechanism is vital for the continuity of the existing micro and macro living organisms in the streams. This mechanism is effected from the existence of metals. In this study, interferences of HgCl2, HgSO4, Ni(NO3)2, CrCl3, CuSO4.5H2O, K2Cr2O7, ZnSO4.7H2O and Al2(SO4)3.18H2O metal compounds on respirometric BOD and related effects on the self purification, are investigated with the representative formations of DO deficit curves. In the presence of these metals, streamwater BOD parameters and related DO deficit curve formations are significantly effected.     

Half-lives of tetra-, penta-, hexa-, hepta-, and octachlorodibenzo-p-dioxin in rats,monkeys, and humans--a critical review

The elimination half-lives (t1/2) in Sprague-Dawley rats for 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), 1,2, 3,7,8-pentachlorodibenzo-p-dioxin (PeCDD), 1,2,3,4,7,8-hexachlorodibenzo-p-dioxin (HxCDD), 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD) and 1,2,3,4,6,7,8,9-octachlorodibenzo-p-dioxin (OCDD) were estimated in long-term studies by Schlatter, Poiger and others. Furthermore, there are some published half-lives of TCDD in adult humans. The average half-life of TCDD in adult humans is approximately 2840 days, while in Sprague-Dawley rats the average t1/2 of TCDD is 19 days. The t1/2 of TCDD in humans is about 150 times that of rats. This factor was used to calculate the t1/2 values of the other polychlorinated dibenzo-p-dioxins (PCDDs) in humans from the rat data. Furthermore, the terminal t1/2 values of PCDDs in adult humans were calculated from the regression equation: logt1/2H = 1.34 logt1/2R + 1.25 which was recently established for 50 xenobiotics (t1/2H = terminal half-lives in days for humans, t1/2R = terminal half-lives in days for rats). The following terminal half-lives in adult humans were obtained: 12.6 years for 1,2,3,7,8-PeCDD, 26-45 years for 1,2,3,4,7,8-HxCDD, 80-102 years for 1,2,3,4,6,7,8-HpCDD and ca. 112-132 years for OCDD. These half-lives of PCDDs are critically compared with measured t1/2 values of PCDDs and other persistent organic pollutants in rats, monkeys and humans.     

Levels of polychlorinated biphenyls, organochlorine pesticides, mercury, cadmium, copper, selenium, arsenic, and zinc in the harbour seal, Phoca vitulina, in Norwegian waters

Residue levels of the chlorinated hydrocarbons polychlorinated biphenyls (PCBs), total DDT, alpha-, beta- and gamma-hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), and oxychlordane in blubber, and the elements mercury, cadmium, copper, selenium, arsenic, and zinc in liver, of 82 harbour seals, Phoca vitulina, were determined. The seals were found dead or dying in Norwegian waters during the disease outbreak caused by a morbilli virus in 1988. Of the chlorinated hydrocarbons, the highest concentrations were found of PCBs, which were 2-4 times higher than the total DDT concentrations. P,p'-DDE was the main contributor to the total DDT, and constituted about 80%. The PCB and total DDT concentrations ranged from 0.4-38 and 0.1-8.8 mg kg(-1), respectively. The mercury concentrations ranged from 0.1-89 mg kg(-1). Significantly higher mean levels of PCBs (13 mg kg(-1) and mercury (16 mg kg(-1)) were found in blubber and liver, respectively, of seals from the Southern coast of Norway, as compared to the corresponding mean levels in seals from the Oslofjord (8.8 and 4.1 mg kg(-1)), and at the Northwestern coast (5.8 and 7.9 mg kg(-1)), respectively. A significant positive correlation was found between the concentrations of selenium and mercury. When the seals were grouped according to sex and age, females of ageclass > 1 and pups of both sexes had significantly lower PCB and total DDT levels than males ageclass > 1. Significantly higher hepatic mercury levels were found in seals ageclass > 1 as compared to pups. Only low levels of the other organochlorines, cadmium and arsenic, were found. Copper and zinc were considered to be present at normal physiological levels. The present organochlorine and heavy metal concentrations gave no support to suggestions that organochlorines and heavy metal pollution may be directly involved in the observed seal deaths.     

Adsorption of Pb,Cd, Cu,Zn, and Ni to titanium dioxide nanoparticles: effect of particle size,solid concentration,and exhaustion

Purpose  

Adsorption of metals (Pb, Cd, Cu, Ni, Zn) to TiO₂ nanoparticles and bulk particles was examined for use as a contaminant removal substrate as a function of particle size, sorbent concentration, and exhaustion.     

A 40+ year record of Cd,Hg, Pb,and U deposition in sediments of Patroon Reservoir,Albany County,NY, USA

Sediments of the Patroon Creek watershed (33 km(2)) are known to contain significant concentrations of heavy metals derived from two industrial sites within the watershed. Mercury Refining, Inc (Mereco) has stored and recycled Hg from 1955 to the present day, and National Lead Industries (NLI) manufactured aircraft components containing Cd, Pb, and U from 1958 to 1984. Here we present the first record of heavy metal deposition as preserved in a 3-m long sediment core collected in 1999 from Patroon Reservoir, a small water body (1.3 ha) downstream of the industrial sites. Bulk sediment samples were collected from the core at 0.05-m intervals and analyzed for total Cd, Pb, and U by ICP-MS and total Hg by CVAAS. Total Hg increases from less than 1 mg kg(-1) (dw) below 1.68 m, to a maximum of 6.2 mg kg(-1) at 0.80 m, and then declines to the sediment-water interface. Total Cd, Pb, and U concentrations increase abruptly above 1.68 m to maximum values of 25, 320, and 3600 mg kg(-1) (dw), respectively, and then decline gradually upwards. By correlating metal profiles with industrial history, we conclude that the 1.68 m horizon was deposited no earlier than 1958, the beginning of aircraft component manufacturing at NLI. The average, apparent sedimentation rate within the reservoir has a minimum value of approximately 0.04 m year(-1) for the 41-year period from 1958 to 1999. In the interval 0--1.68 m, average concentrations of Cd, Hg, Pb, and U are 1.69, 1.50, 461, and 13 mg kg(-1), respectively. These levels are comparable with other lake, reservoir and stream sediments that have been moderately to severely impacted by industrial pollution and are above levels expected to be detrimental to aquatic organisms.     

Lead,mercury, cadmium,chromium, nickel,copper, zinc,calcium, iron,manganese and chromium (VI) levels in Nigeria and United States of America cement dust

This study was aimed at investigating the relative abundance of heavy metals in cement dust from different cement dust factories in order to predict their possible roles in the severity of cement dust toxicity. The concentrations of total mercury (Hg), copper (Cu), chromium (Cr), cadmium (Cd), nickel (Ni), manganese (Mn), lead (Pb), iron (Fe) and chromium (VI) (Cr (VI)) levels in cement dust and clinker samples from Nigeria and cement dust sample from the United States of America (USA) were determined using graphite furnace atomic absorption (GFAAS), while Zn and Ca were measured by flame atomic absorption spectrophotometry (FAAS), and Cr (VI) by colorimetric method. Total Cu, Ni and Mn were significantly higher in cement dust sample from USA (p < 0.05), also, both total Cr and Cr (VI) were 5.4–26 folds higher in USA cement dust compared with Nigeria cement dust or clinker (p < 0.001). Total Cd was higher in both Nigeria cement dust and clinker (p < 0.05 and p < 0.001), respectively. Mercury was more in both Nigeria cement dust and clinker (p < 0.05), while Pb was only significantly higher in clinker from Nigeria (p < 0.001). These results show that cement dust contain mixture of metals that are known human carcinogens and also have been implicated in other debilitating health conditions. Additionally, it revealed that metal content concentrations are factory dependent. This study appears to indicate the need for additional human studies relating the toxicity of these metals and their health impacts on cement factory workers.     

Toxicity, dioxin-like activities, and endocrine effects of DDT metabolites—DDA, DDMU, DDMS, and DDCN

Background, aim, and scope  

2,2-bis(chlorophenyl)-1,1,1-trichloroethane (DDT) metabolites, other than those routinely measured [i.e., 2,2-bis(chlorophenyl)-1,1-dichloroethylene (DDE) and 2,2-bis(chlorophenyl)-1,1-dichloroethane (DDD)], have recently been detected in elevated concentrations not only in the surface water of Teltow Canal, Berlin, but also in sediment samples from Elbe tributaries (e.g., Mulde and Havel/Spree). This was paralleled by recent reports that multiple other metabolites could emerge from the degradation of parent DDT by naturally occurring organisms or by interaction with some heavy metals. Nevertheless, only very few data on the biological activities of these metabolites are available to date. The objective of this communication is to evaluate, for the first time, the cytotoxicity, dioxin-like activity, and estrogenicity of the least-studied DDT metabolites.     

Effects of elevated CO2, nitrogen supply and tropospheric ozone on spring wheat-II. Nutrients (N, P, K, S, Ca, Mg, Fe, Mn, Zn)

CO(2) enrichment is expected to alter leaf demand for nitrogen and phosphorus in plant species with C(3) carbon dioxide fixation pathway, thus possibly causing nutrient imbalances in the tissues and disturbance of distribution and redistribution patterns within the plants. To test the influence of CO(2) enrichment and elevated tropospheric ozone in combination with different nitrogen supply, spring wheat (Tritium aestivum L. cv. Minaret) was exposed to three levels of CO(2) (361, 523, and 639 microl litre(-1), 24 h mean from sowing to final harvest), two levels of ozone (28.4 and 51.3 nl litre(-1)) and two levels of nitrogen supply (150 and 270 kg ha(-1)) in a full-factorial design in open-top field chambers. Additional fertilization experiments (120, 210, and 330 kg N ha(-1)) were carried out at low and high CO(2) levels. Macronutrients (N, P, K, S, Ca, Mg) and three micronutrients (Mn, Fe, Zn) were analysed in samples obtained at three different developmental stages: beginning of shoot elongation, anthesis, and ripening. At each harvest, plant samples were separated into different organs (green and senescent leaves, stem sections, ears, grains). According to analyses of tissue concentrations at the beginning of shoot elongation, the plants were sufficiently equipped with nutrients. Elevated ozone levels neither affected tissue concentrations nor shoot uptake of the nutrients. CO(2) and nitrogen treatments affected nutrient uptake, distribution and redistribution in a complex manner. CO(2) enrichment increased nitrogen-use efficiency and caused a lower demand for nitrogen in green tissues which was reflected in a decrease of critical nitrogen concentrations, lower leaf nitrogen concentrations and lower nitrogen pools in the leaves. Since grain nitrogen uptake during grain filling depended completely on redistribution from vegetative pools in green tissues, grain nitrogen concentrations fell considerably with severe implications for grain quality. Ca, S, Mg and Zn in green tissues were influenced by CO(2) enrichment in a similar manner to nitrogen. Phosphorus concentrations in green tissues, on the other hand, were not, or only slightly, affected by elevated CO(2). In stems, 'dilution' of all nutrients except manganese was observed, caused by the huge accumulation of water soluble carbohydrates, mainly fructans, in these tissues under CO(2) enrichment. Whole shoot uptake was either remarkably increased (K, Mn, P, Mg), nearly unaffected (N, S, Fe, Zn) or decreased (Ca) under CO(2) enrichment. Thus, nutrient cycling in plant-soil systems is expected to be altered under CO(2) enrichment.     

Toxicity of mancozeb,chlorothalonil, captan,fluopyram, boscalid,and difenoconazole to Didymella applanata isolates from Serbia

Field isolates of Didymella applanata, the causal agent of spur blight of raspberry, were evaluated in vitro for their sensitivity to mancozeb, chlorothalonil, captan, fluopyram, boscalid and difenoconazole. A total of 10 isolates, collected during 2013 at five localities in the major raspberry growing region in Serbia, and characterized as copper hydroxide, dithianon, and tebuconazole (sensitive), pyraclostrobin (sensitive or highly resistant) and fluazinam (sensitive or moderately resistant), were used in this study. The EC₅₀ values for the isolates ranged from 1.33 to 2.88 mg L^?1 for mancozeb, from 3.18 to 6.65 mg L^?1 for chlorothalonil, from 15.75 to 24.69 mg L^?1 for captan and from 1.80 to 8.20 mg L^?1 for fluopyram. The narrowest range of EC₅₀ values was recorded for difenoconazole (0.23–0.49 mg L^?1), whereas the widest range was obtained for boscalid (4.49–49.25 mg L^?1). The calculated resistance factors showed that all D. applanata isolates were sensitive to mancozeb, chlorothalonil, captan, and difenoconazole. Four isolates were moderately resistant to boscalid, while three of them were also moderately resistant to fluopyram. This finding of moderately resistant isolates to these SDHI fungicides indicates a possible cross-resistance which should be clarified in further investigations.