Formation, release and control of dioxins in cement kilns

Co-processing of hazardous wastes in cement kilns have for decades been thought to cause increased emissions of PCDD/PCDFs--a perception that has been evaluated in this study. Hundreds of PCDD/PCDF measurements conducted by the cement industry and others in the last few years, on emissions and solid materials, as well as recent test burns with hazardous wastes in developing countries do not support this perception. Newer data has been compared with older literature data and shows in particular that many emission factors have to be reconsidered. Early emission factors for cement kilns co-processing hazardous waste, which are still used in inventories, are shown to be too high compared with actual measurements. Less than 10 years ago it was believed that the cement industry was the main contributor of PCDD/PCDFs to air; data collected in this study indicates however that the industry contributes with less than 1% of total emissions to air. The Stockholm Convention on POPs presently ratified by 144 parties, classifies cement kilns co-processing hazardous waste as a source category having the potential for comparatively high formation and release of PCDD/PCDFs. This classification is based on early investigations from the 1980s and 1990s where kilns co-processing hazardous waste had higher emissions compared to those that did not burn hazardous waste. However, the testing of these kilns was often done under worst case scenario conditions known to favour PCDD/PCDF formation. More than 2000 PCDD/PCDF cement kiln measurements have been evaluated in this study, representing most production technologies and waste feeding scenarios. They generally indicate that most modern cement kilns co-processing waste today can meet an emission level of 0.1ngI-TEQ/m(3), when well managed and operated. In these cases, proper and responsible use of waste including organic hazardous waste to replace parts of the fossil fuel does not seem to increase formation of PCDD/PCDFs. Modern preheater/precalciner kilns generally seems to have lower emissions than older wet-process cement kilns. It seems that the main factors stimulating formation of PCDD/PCDFs is the availability of organics in the raw material and the temperature of the air pollution control device. Feeding of materials containing elevated concentrations of organics as part of raw-material-mix should therefore be avoided and the exhaust gases should be cooled down quickly in long wet and long dry cement kilns without preheating. PCDD/PCDFs could be detected in all types of solid samples analysed: raw meal, pellets and slurry; alternative raw materials as sand, chalk and different ashes; cement kiln dust, clinker and cement. The concentrations are however generally low, similar to soil and sediment.     

The function of digestive enzymes on Cu, Zn, and Pb release from soil in in vitro digestion tests

The bioaccessibility of soil heavy metals is the solubility of soil heavy metals in synthetic human digestive juice, which is usually determined using in vitro digestion test. To reveal the effects of digestive enzymes on soil heavy metals bioaccessibility, three representative in vitro digestion tests, Simple Bioaccessibility Extraction Test (SBET), Physiologically Based Extraction Test (PBET), and Simple Gastrointestinal Extraction Test (SGET), were chosen. The bioaccessibility of soil Cu, Zn, and Pb in each method were respectively evaluated with and without digestive enzymes, and the differences were compared. The results showed that the effects of digestive enzymes varied with different methods and elements. Because of digestive enzymes addition, the environmental change from acid gastric phase to neutral intestinal phase of PBET did not result in apparently decrease of the bioaccessibility of soil Cu. However, the solubility of soil Zn and Pb were pH-dependent. For SGET, when digestive enzymes were added, its results reflected more variations resulting from soil and element types. The impacts of digestive enzymes on heavy metal dissolution are mostly seen in the intestinal phase. Therefore, digestive enzyme addition is indispensable to the gastrointestinal digestion methods (PBET and SGET), while the pepsin addition is not important for the methods only comprised of gastric digestion (SBET).     

Controlled release, blind test of DNAPL remediation by ethanol flushing

A dense nonaqueous phase liquid (DNAPL) source zone was established within a sheet-pile isolated cell through a controlled release of perchloroethylene (PCE) to evaluate DNAPL remediation by in-situ cosolvent flushing. Ethanol was used as the cosolvent, and the main remedial mechanism was enhanced dissolution based on the phase behavior of the water-ethanol-PCE system. Based on the knowledge of the actual PCE volume introduced into the cell, it was estimated that 83 L of PCE were present at the start of the test. Over a 40-day period, 64% of the PCE was removed by flushing the cell with an alcohol solution of approximately 70% ethanol and 30% water. High removal efficiencies at the end of the test indicated that more PCE could have been removed had it been possible to continue the demonstration. The ethanol solution extracted from the cell was recycled during the test using activated carbon and air stripping treatment. Both of these treatment processes were successful in removing PCE for recycling purposes, with minimal impact on the ethanol content in the treated fluids. Results from pre- and post-flushing partitioning tracer tests overestimated the treatment performance. However, both of these tracer tests missed significant amounts of the PCE present, likely due to inaccessibility of the PCE. The tracer results suggest that some PCE was inaccessible to the ethanol solution which led to the inefficient PCE removal rates observed. The flux-averaged aqueous PCE concentrations measured in the post-flushing tracer test were reduced by a factor of 3 to 4 in the extraction wells that showed the highest PCE removal compared to those concentrations in the pre-flushing tracer test.     

Controlled release,blind tests of DNAPL characterization using partitioning tracers

The partitioning tracer technique for dense nonaqueous phase liquid (DNAPL) characterization was evaluated in an isolated test cell, in which controlled releases of perchloroethylene (PCE) had occurred. Four partitioning tracer tests were conducted, two using an inverted, double five-spot pumping pattern, and two using vertical circulation wells. Two of the four tests were conducted prior to remedial activities, and two were conducted after. Each test was conducted as a "blind test" where researchers conducting the partitioning tracer tests had no knowledge of the volume, method of release, nor resulting spatial distribution of DNAPL. Multiple partitioning tracers were used in each test, and the DNAPL volume estimates varied significantly within each test based on the different partitioning tracers. The tracers with large partitioning coefficients generally predicted a smaller volume of PCE than that expected based on the actual release volume. However, these predictions were made for low DNAPL saturations (average saturation was approximately 0.003), under conditions near the limits of the method's application. Furthermore, there were several factors that may have hindered prediction accuracy, including tracer degradation and remedial fluid interference.     

不同pH控制策略下剩余污泥中NH4^＋-N、PO4^3--P、COD溶出研究

污水处理厂的剩余污泥中富含氮、磷、COD,在其水解酸化过程中对pH条件进行控制,使污泥中的氮、磷、COD溶出到上清液中并进行回收利用是可行的。在22～25℃的温度条件下,1#反应器中剩余污泥先调节为酸性（pH=3）,在实验第8 d氨氮、磷酸盐溶出量最多后调节为碱性（pH=10）;3#反应器中剩余污泥先调节为碱性（pH=10）,在实验第8 dCOD溶出量最多后调节为酸性（pH=3）;2#反应器为对照实验,pH不进行调节。结果表明：若要以回收污泥中的氨氮、磷酸盐为主,剩余污泥由碱性（pH=10）调节为酸性（pH=3）优于由酸性（pH=3）调节为碱性（pH=10）;若要回收污泥上清液中的COD为主,剩余污泥由酸性（pH=3）调节为碱性（pH=10）优于由碱性（pH=10）调节为酸性（pH=3）。     

Accumulation, transformation, and release of inorganic arsenic by the freshwater cyanobacterium Microcystis aeruginosa

Arsenic (As) as a major hazardous metalloid was affected by phytoplankton in many aquatic environments. The toxic dominant algae Microcystis aeruginosa was exposed to different concentrations of inorganic arsenic (arsenate or arsenite) for 15 days in BG11 culture media. Arsenic accumulation, toxicity, and speciation in M. aeruginos as well as the changes of As species in media were examined. M. aeruginosa has a general well tolerance to arsenate and a definite sensitivity to arsenite. Additionally, arsenate actively elevated As methylation by the algae but arsenite definitely inhibited it. Interestingly, the uptake of arsenite was more pronounced than that of arsenate, and it was correlated to the toxicity. Arsenate was the predominant species in both cells and their growth media after 15 days of exposure to arsenate or arsenite. However, the amount of the methylated As species in cells was limited and insignificantly affected by the external As concentrations. Upon uptake of the inorganic arsenic, significant quantities of arsenate as well as small amounts of arsenite, DMA, and MMA were produced by the algae and, in turn, released back into the growth media. Bio-oxidation was the first and primary process and methylation was the minor process for arsenite exposures, while bioreduction and the subsequent methylation were the primary metabolisms for arsenate exposures. Arsenic bioaccumulation and transformation by M. aeruginosa in aquatic environment should be paid more attention during a period of eutrophication.     

Effect of slow release nitrogenous fertilizers and biochar on growth,physiology, yield,and nitrogen use efficiency of sunflower under arid climate

Environmental Science and Pollution Research - Sunflower plants need nitrogen consistently and in higher amount for optimum growth and development. However, nitrogen use efficiency (NUE) of...     

Arsenic release from flooded paddy soils is influenced by speciation, Eh, pH, and iron dissolution

Arsenic (As) is highly mobilized when paddy soil is flooded, causing increased uptake of As by rice. We investigated factors controlling soil-to-solution partitioning of As under anaerobic conditions. Changes in As and iron (Fe) speciation due to flooded incubation of two paddy soils (soils A and B) were investigated by HPLC/ICP-MS and XANES. The flooded incubation resulted in a decrease in Eh, a rise in pH, and an increase in the As(III) fraction in the soil solid phase up to 80% of the total As in the soils. The solution-to-soil ratio of As(III) and As(V) (R_L/S) increased with pH due to the flooded incubation. The R_L/S for As(III) was higher than that for As(V), indicating that As(III) was more readily released from soil to solution than was As(V). Despite the small differences in As concentrations between the two soils, the amount of As dissolved by anaerobic incubation was lower in soil A. With the development of anaerobic conditions, Fe(II) remained in the soil solid phase as the secondary mineral siderite, and a smaller amount of Fe was dissolved from soil A than from soil B. The dissolution of Fe minerals rather than redox reaction of As(V) to As(III) explained the different dissolution amounts of As in the two paddy soils. Anaerobic incubation for 30 d after the incomplete suppression of microbial activity caused a drop in Eh. However, this decline in Eh did not induce the transformation of As(V) to As(III) in either the soil solid or solution phases, and the dissolution of As was limited. Microbial activity was necessary for the reductive reaction of As(V) to As(III) even when Eh reached the condition necessary for the dominance of As(III). Ratios of released As to Fe from the soils were decreased with incubation time during both anaerobic incubation and abiotic dissolution by sodium ascorbate, suggesting that a larger amount of As was associated with an easily soluble fraction of Fe (hydr) oxide in amorphous phase and/or smaller particles.     

Pesticide storage and release in unsaturated soil in Illinois, USA.

The chemical fate and movement of pesticides may be subject to transient storage in unsaturated soils during periods of light rainfall, and subsequent release into shallow groundwater by increased rainfall. The objective of this study was to conduct field-scale experiments to determine the relative importance of transient storage and subsequent release of agrichemicals from the vadose zone into potential aquifers. Two field-scale experiments were conducted under a rain exclusion shelter. In the 1x experiment, atrazine and chlorpyrifos were applied at application-rate equivalents (1.6 kg ha(-1) and 1.3 kg ha(-1), respectively). In the 4x experiment, atrazine was applied in an amount that was four times greater than that usually applied to fields (6.7 kg ha(-1)). Water was either applied to simulate rain or withheld to simulate dry periods. In the 1x experiment, atrazine was detected in the water samples whereas chlorpyrifos was not detected in the majority of the samples. The dry period imposed on the treatment plot did not appear to result in storage of the chemicals, whereas the wet period resulted in greater leaching of atrazine, although the concentrations remained less than the Maximum Contaminant Level of 3 microg L(-1). Both chemicals were detected in soil samples collected from a 20- to 30-cm depth, but it appeared that both chemicals dissipated before the field experiment was concluded. It appeared that the one-time application of atrazine and chlorpyrifos at the label rates did not result in a sufficient mass to be stored and flushed in significant concentrations to the saturated zone. When atrazine was applied at 4x and a longer drought period was imposed on the treatment plot, the resulting concentrations of dissolved atrazine were still less than 3 microg L(-1) . Atrazine was detected in only the near-surface (0 to 15 cm) soil samples and the herbicide dissipated before the onset of the dry period in the treatment plot. The results of this field study demonstrated that atrazine and chlorpyrifos were not sufficiently persistent to be stored and then released in significantly large concentrations to the saturated zone. The dissipation half-life of atrazine in the 4x application was about 44 days. This study, in addition to others, suggested that atrazine may be less persistent in surface soil than has been generally reported.     

不同pH控制策略下剩余污泥中NH+4-N、PO3-4-P、COD溶出研究

污水处理厂的剩余污泥中富含氮、磷、COD，在其水解酸化过程中对pH条件进行控制，使污泥中的氮、磷、COD溶出到上清液中并进行回收利用是可行的。在22~25℃的温度条件下,1#反应器中剩余污泥先调节为酸性（pH=3），在实验第8 d氨氮、磷酸盐溶出量最多后调节为碱性（pH=10）；3#反应器中剩余污泥先调节为碱性（pH=10），在实验第8 d COD溶出量最多后调节为酸性(pH=3)； 2#反应器为对照实验，pH不进行调节。结果表明：若要以回收污泥中的氨氮、磷酸盐为主，剩余污泥由碱性（pH=10）调节为酸性（pH=3）优于由酸性（pH=3）调节为碱性（pH=10）；若要回收污泥上清液中的COD为主，剩余污泥由酸性（pH=3）调节为碱性（pH=10）优于由碱性（pH=10）调节为酸性（pH=3）。     

Effect of overlying water pH, dissolved oxygen, salinity and sediment disturbances on metal release and sequestration from metal contaminated marine sediments

Experiments were undertaken to examine the key variables affecting metal release and sequestration processes in marine sediments with metal concentrations in sediments reaching up to 86, 240, 700, and 3000 mg kg(-1) (dry weight) for Cd, Cu, Pb and Zn, respectively. The metal release and sequestration rates were affected to a much greater extent by changes in overlying water pH (5.5-8.0) and sediment disturbance (by physical mixing) than by changes in dissolved oxygen concentration (3-8 mg l(-1)) or salinity (15-45 practical salinity units). The physical disturbance of sediments was also found to release metals more rapidly than biological disturbance (bioturbation). The rate of oxidative precipitation of released iron and manganese increased as pH decreased and appeared to greatly influence the sequestration rate of released lead and zinc. Released metals were sequestered less rapidly in waters with lower dissolved oxygen concentrations. Sediments bioturbated by the benthic bivalve Tellina deltoidalis caused metal release from the pore waters and higher concentrations of iron and manganese in overlying waters than non-bioturbated sediments. During 21-day sediment exposures, T. deltoidalis accumulated significantly higher tissue concentrations of cadmium, lead and zinc from the metal contaminated sediments compared to controls. This study suggests that despite the fact that lead and zinc were most likely bound as sulfide phases in deeper sediments, the metals maintain their bioavailability because of the continued cycling between pore waters and surface sediments due to physical mixing and bioturbation.     

Influence of algal bloom degradation on nutrient release at the sediment–water interface in Lake Taihu, China

Algal bloom could drastically influence the nutrient cycling in lakes. To understand how the internal nutrient release responds to algal bloom decay, water and sediment columns were sampled at 22 sites from four distinct regions of China’s eutrophic Lake Taihu and incubated in the laboratory to examine the influence of massive algal bloom decay on nutrient release from sediment. The column experiment involved three treatments: (1) water and sediment (WS); (2) water and algal bloom (WA); and (3) water, sediment, and algal bloom (WSA). Concentrations of dissolved oxygen (DO), total nitrogen (TN), total phosphorus (TP), ammonium (NH ₄ ⁺ -N), and orthophosphate (PO ₄ ^3? -P) were recorded during incubation. The decay of algal material caused a more rapid decrease in DO than in the algae-free controls and led to significant increases in NH ₄ ⁺ -N and PO ₄ ^3? -P in the water. The presence of algae during the incubation had a regionally variable effect on sediment nutrient profiles. In the absence of decaying algae (treatment WS), sediment nutrient concentrations decreased during the incubation. In the presence of blooms (WSA), sediments from the river mouth released P to the overlying water, while sediments from other regions absorbed surplus P from the water. This experiment showed that large-scale algal decay will dramatically affect nutrient cycling at the sediment–water interface and would potentially transfer the function of sediment as “container” or “supplier” in Taihu, although oxygen exchange with atmosphere in lake water was stronger than in columns. The magnitude of the effect depends on the physical–chemical character of the sediments.     

四平市二龙湖底泥磷释放研究

采用室内实验模拟法对四平市二龙湖富营养化限制因子磷的底泥释放速率及释放量进行了研究,并研究在种环境因子(温度、pH、DO和扰动因素)影响下底泥磷的释放规律。结果表明,(1)二龙湖年平均底泥释磷量为208·78g,最大释磷率为0·889μg/g(T=20℃,pH=8,DO为4·68mg/L);(2)自然和人为的扰动因素会促进底泥的磷释放;(3)H在弱酸至中性范围内底泥释磷量最小,酸性和碱性条件都有利于磷的释放;(4)随着温度的升高底泥释磷量增大;(5)厌条件比好氧条件更有利于磷的释放。     

四平市二龙湖底泥磷释放研究

采用室内实验模拟法对四平市二龙湖富营养化限制因子磷的底泥释放速率及释放量进行了研究,并研究在各种环境因子（温度、pH、DO和扰动因素）影响下底泥磷的释放规律.结果表明,（1）二龙湖年平均底泥释磷量为208.78kg,最大释磷率为0.889 μg/g（T=20℃,pH=8,DO为4.68 mg/L）;（2）自然和人为的扰动因素会促进底泥的磷释放;（3）pH在弱酸至中性范围内底泥释磷量最小,酸性和碱性条件都有利于磷的释放;（4）随着温度的升高底泥释磷量增大;（5）厌氧条件比好氧条件更有利于磷的释放.     

Sediment characteristics,phosphorus types and phosphorus release rates between river and lake sediments

The Han river is 469.7 km long with 26219-km2 area watershed, and is the primary drinking water source for the 20 million people that live in Seoul, Kangwon-Do and Kyunggi-Do, Korea. Phosphorus release from sediments impacts water quality, and is endangering the beneficial use of the river. This research measures phosphorus release and predicts future releases from bottom sediments of two tributary areas (Chungpyung Lake (CPL) and Jamsil submerged dam (JSD) area in the Han river). Sediment samples were taken over a 4-year period from four points in the Jamsil dam area and from 92 points in CPL. The sediments were analyzed for total phosphorus, the form of the phosphorus and release rates under different conditions to the water column. Sediment phosphorus distribution from CPL was 3-5% adsorbed-P (Ads-P), 15-20% non-apatite-P (NAI-P), 25-30% apatite-P (A-P) and 45-57% residual-P (R-P). In the JSD area, the phosphorus distribution ranges were 1-3% Ads-P, 22-39% NAI-P, 26-40% A-P and 30-39% R-P. Laboratory experiments showed that phosphorus release rates from 60 to 80 mg/m2 week in JSD area and ranged from 25 to 40 mg/m2 week in CPL sediments.     

Effects of uncontrolled particulate matter release on precipitation under warfare conditions

This study has shown theoretical, observed and experimental evidence of pollutants released, transported and deposited during the Kosovo conflict in 1999 and their effects on precipitation in Serbia. The greatest bombardment of the chemical industry, oil refineries and fuel storage in Serbia which occurred during April, resulted in releases of many hazardous, toxic and cancerogenic substances. The number of April's days with precipitation greater or equal to 0.1 mm in 1999 are compared to those in the period from 1961 to 1990 registered at thirty meteorological stations in Serbia and especially at the Belgrade-Observatory station in the period from 1888 to 1995. The maximums of days with precipitation greater or equal to 0.1 mm were at the wider Belgrade area and at the central and southwestern parts of Serbia during April 1999. This is confirmed by using the Eta trajectory analysis.     

Source and release mechanism of arsenic in aquifers of the Mekong Delta, Vietnam

In order to elucidate the arsenic source and its release mechanism into groundwater in the Mekong Delta, Vietnam, groundwater samples were collected from wells at different depths (20 to 440 m) and core samples (from 20 to 265 m depth) were analyzed. Based on the analytical results for groundwater and core samples, the As source in groundwater is considered to be pyrite (FeS(2)) in acid sulfate soil (ASS) under oxidizing conditions and hydrous ferric oxide (Fe(OH)(3)) under reducing conditions. Geochemical modeling demonstrated that As(III) is the dominant species and the presence of As-bearing sulfides, Fe-bearing sulfides and oxides phases may locally act as potential sinks for As. From variation between Fe and As concentrations in groundwater samples, the release mechanism of As is: dissolution of Fe(OH)(3) containing As under reducing conditions and oxidative decomposition of FeS(2) containing As under oxidizing conditions.     

pH值对烧结砖中重金属释放的影响

采用酸消解实验和NEN 7371浸出实验研究了烧结砖中重金属总量和有效释放量,采用pH-dependence实验研究pH对破碎烧结砖样品中重金属(Cr、Ni、As、Cd和Pb)浸出特性的影响,以及烧结砖样品的酸碱缓冲容量。结果表明,烧结砖中重金属的有效释放量低于总量,释放率从大到小依次为CdAsPbNiCr;烧结砖的酸缓冲容量较小,浸出液pH从7.03降到3.64,消耗了29.33 mmol/kg硝酸,碱缓冲容量较大,pH从7.03升到12.40,共消耗256 mmol/kg氢氧化钠溶液,因此在使用烧结砖的过程中要特别注意环境pH;浸提液的酸碱性是影响烧结砖中重金属浸出的重要参数,在实验研究的pH范围内,不同重金属的浸出规律不同。Cr和As的释放受pH影响较小,而Ni和Cd的浸出量随pH的增大而降低,Pb的浸出量在强酸和强碱条件下均较大,当pH在5.59~9.86的范围内浸出量很低。     

模拟酸雨对土壤盐基离子的淋溶释放影响

选取南方主要酸沉降区土壤作模拟酸雨淋溶实验,探讨在酸雨作用下各土壤随降水酸度、降水过程及 降水量的变化其盐基离子的淋溶特性及影响因素。     

赤泥在控制沉积物磷释放中的应用研究

利用烧结法赤泥中富含Ca、Fe等金属元素的氧化物而具有吸附性的特点，通过室内模拟研究赤泥投加对沉积物中各种磷形态含量及分布比例的影响，进而探讨利用赤泥控制沉积物中磷释放的可行性。对经过处理后的沉积物磷形态分析后表明，投加赤泥能促使沉积物中铁铝磷向钙磷转化（Pearson相关分析，r=-0.892，P<0.01，n=9），且赤泥的强碱性使沉积物pH值逐渐升高。确定了赤泥最佳投加比例为5%，此时沉积物的pH为9.03，铁铝磷含量由初始的148 mg/kg降至107 mg/kg，占总磷比例也由18.1%降至13.4%，钙磷含量由486 mg/kg升至546 mg/kg，其占总磷比例则由60%增至68.7%，铁铝磷和钙磷之间的转化已基本完成，继续增加赤泥投加量对沉积物中磷形态间的相互转化影响甚微。由于铁铝磷较钙磷活性高而易释放，可见投加赤泥能降低沉积物中磷的释放风险。赤泥可以作为吸附材料被应用于沉积物磷污染控制技术中，为有效控制水体内源磷负荷提供一种新思路和廉价材料。