Effects of additives on solidification of API separator sludge

API separator sludge was solidified with various combinations of binders and absorbent soil additives. The binders utilized were Type I Portland Cement, Type C Flyash, and a 1:1 combination of the two. The soil additives used were bentonite, diatomite, Fuller's earth, and two brands of chemically altered bentonites, or organoclays. The effectiveness of the solidification materials was based on their effect on the physical and leaching characteristics of the sludge.It was determined the Portland cement and combination binders provided the sludge with adequate physical and strength characteristics. It was also determined the affinity of each additive for water had an important influence on the physical characteristics of the solidified sludge. The results of the leaching procedure indicated the binders alone reduced the leachability of organic constituents from the sludge by 1/5 to 1/10. It appeared the use of the additives with the binders may have further reduced the leachability of constituents from sludge, with the incorporation of the organoclay additives further reducing leachability by up to 1/2. Also, it appeared the absorbing capacity of the additives was directly related to their ability to reduce the leachability of organic constituents from the sludge.     

化学需氧量和总有机碳在水质在线监测中的比较

化学需氧量（COD）和总有机碳（TOC）是定量表示水体受有机物污染的2个重要代表性指标。传统的COD在线监测方法在监测有机污染物方面存在一定的挑战,系统比较了COD和TOC在线监测方法在特殊水质中的应用。结果显示：TOC对难氧化有机物的氧化效率高达98%,高氯离子和无机还原性离子对TOC测量误差影响分别约为10%和7%。TOC可更直接、更准确地反映出水体受有机物污染的情况,最后对TOC指标在水质在线监测中的推广应用提出建议。     

浅谈TOC与CODCr的关系

介绍了TOC和CODCr的含义，比较了TOC与CODCr测定方法、使用仪器的不同和各自的优缺点，并从理论上和实际水样测定中论述了TOC和CODCr的相关性。对于不同的废水，TOC 与CODCr的相关性不一样，必须先实验求出二者之间的关系。     

COD与TOC测定方法的比较

系统地对比了 COD和 TOC 两种水中有机污染指标测定方法原理，得出了 TOC 在直接代表水质有机污染、氧化有机物完全、产生二次污染物少、测定时间短和消耗劳动力少等方面优于 COD 的结论，并分析了 TOC 取代 COD 的难点和趋势。     

Evaluation of old landfills--a thermoanalytical and spectroscopic approach

Abandoned landfills and dumps, where untreated waste materials were deposited in the past, are a main anthropogenic source of relevant gaseous emissions. The determination of stability is a crucial target in the context of landfill risk assessment. FTIR spectroscopy and simultaneous thermal analysis in association with multivariate statistical methods were applied to landfill materials in order to get information on the kind of waste and its reactivity. The spectral and thermal patterns are fingerprints of the material. Industrial waste and the material from a 5-year-old reactor landfill were distinguished from the defined classes of mechanically-biologically treated ("MBT") waste and 30 to 40-year-old stable landfills containing municipal solid waste and construction waste ("LF") by a classification model based on soft independent modeling of class analogy (SIMCA). Degradation experiments were carried out with the fresh material originating from one MBT plant that was subjected to aerobic and anaerobic conditions in lab-scale reactors. These samples were compared to samples of one reactor landfill and to the landfill fraction from the MBT plant to demonstrate the efficiency of the biological pretreatment before final disposal. Prediction models that are based on spectral or thermal characteristics and the corresponding reference analyses were calculated by means of a partial least squares regression (PLS-R). The developed models of the biological oxygen demand (BOD) and the dissolved organic carbon (DOC) were based on spectral data, the models of the total organic carbon (TOC) and total nitrogen (TN) were based on thermal data (heat flow profiles and mass spectra of combustion gases). Preliminary results are discussed. The enthalpy of the materials decreases with progressing mineralization, whereas the enthalpy of the remaining organic matter increases. The ratio of the enthalpies was used as an indicator of stability. Selected samples comprising old landfills, a recent reactor landfill, MBT landfills and MBT materials were classified according to the calculated ratios.     

Leaching of nitrogen, phosphorus, TOC and COD from the biosolids of the municipal wastewater treatment plant of Thessaloniki

Biosolids from the WWTP of Thessaloniki were examined for the leaching of phosphorus (as ), nitrogen (as and ), and organic matter (as TOC and COD), using two tests: (1) a pH static leaching test and (2) a characterization test, relating contaminant release to the liquid to solid (L/S) ratio. Moreover, a Microtox toxicity test was conducted, to examine the pH dependency of the toxicity of the sludge leachate on the Vibrio fischeri bacterium. Maximum phosphorus release was observed at pH < 3 and at pH > 10. Ammonium nitrogen exhibited maximum leachability at near neutral pH conditions, while nitrate nitrogen exhibited a mild increase in the leachate, as the leachant pH increased from 2 to 12. Both TOC and COD exhibited an increase in the leachate concentration, as the leachant pH was increased from 2 to 12. Ecotoxicological analysis showed that maximum toxicity occurred at very low and very high pH-conditions. As liquid-to-solid ratio increased, the leachate concentration (in mg/l) of all parameters studied decreased. The results of the study were used to conduct a release assessment estimate for the case of Thessaloniki.     

Evaluating the Applicability of Regulatory Leaching Tests for Assessing Lead Leachability in Contaminated Shooting Range Soils

The toxicity characteristic leaching procedure (TCLP) is the current US-EPA standard protocol to evaluate metal leachability in wastes and contaminated soils. However, application of TCLP to assess lead (Pb) leachability from contaminated shooting range soils may be questionable. This study determined Pb leachability in the range soils using TCLP and another US-EPA regulatory leaching method, synthetic precipitation leaching procedure (SPLP). Possible mechanisms that are responsible for Pb leaching in each leaching protocol were elucidated via X-ray diffraction (XRD). Soil samples were collected from the backstop berms at four shooting ranges, with Pb concentrations ranging from 5,000 to 60,600 mg kg⁻¹ soil. Lead concentrations in the TCLP leachates were from 3 to 350 mg l⁻¹, with all but one soil exceeding the USEPA non-hazardous waste disposal limit of 5 mg l⁻¹. However, continued dissolution of metallic Pb particles from spent Pb bullets and its re-precipitation as cerussite (PbCO₃) prevented the TCLP extraction from reaching equilibrium at the end of the standard leaching period (18 h). Thus, the standard one-point TCLP test would either over- or under-estimate Pb leachability in shooting range soils. Lead concentration in the SPLP leachates ranged from 0.021 to 2.6 mg l⁻¹, with all soils above the USEPA regulatory limit of 0.015 mg l⁻¹. In contrast to TCLP, SPLP leaching had reached equilibrium, with regard to both pH and Pb concentrations, within the standard 18 h leaching period, and the analytical SPLP results were in good agreement with those derived from modeling. Thus, we concluded that SPLP is a more appropriate alternative than TCLP for assessing lead leachability in range soils.     

水体中TOC与COD相关性研究

针对不同地区的地表水、生活污水和工业废水的TOC和COD进行了测试,对测定值进行线性回归分析。结果表明,不同类型的水体其TOC与COD均具有一定的相关性,尤其是生活污水和工业废水,TOC与COD相关性比较显著,在一定条件下可由测定的TOC值推算出COD值。     

Study of leachability and fractional alteration of arsenic and co-existing elements in stabilized contaminated sludge using a flow-through extraction system

This study investigates the stabilization of As in the contaminated sludge after treatment with MnO(2) or Ca(OH)(2), and the influence of the stabilizing materials on the leachability of the co-existing elements Pb and Zn. By exploiting a continuous-flow assembly facilitating a modified Wenzel's sequential extraction scheme (designed for the fractionation of arsenic), it is possible to ascertain the leachability, mobility and fractional alteration of these elements under stimulated natural (flow-through) leaching conditions. The fractionation data show that more than 80% of As, Pb and Zn in the untreated sludge are bound in the amorphous Fe oxides fraction and residual fraction. The addition of MnO(2) has only an insignificant effect on As fractional transformation, while Ca(OH)(2) caused an increase in As mobility. For Pb, the decrease in leachability was clearly visible. The extractable Pb was reduced by 18% and 40% in stabilized MnO(2) and Ca(OH)(2) sludge samples, respectively. Unlike that of Pb, the mobility of Zn was not affected by the additives used. Their fractional distribution patterns before and after the stabilization process remained the same. The ability to produce detailed leaching profiles for As and other elements (Pb, Zn, Ca, Mn and Fe) meant that elemental associations in individual fractions could be examined. From the MnO(2)-treated sludge, the coincidence of the As, Pb, Zn, Fe, and Mn peaks seems to indicate a close association of these elements in the Fe-oxides-bound fraction. Furthermore, the leaching profiles may be used as evidence of a strong affinity between these elements and added MnO(2).     

Screening of dioxin-like compounds in bio-composts and their materials: chemical analysis and fractionation-directed evaluation of AhR ligand activities using an in vitro bioassay

Application of the dioxin responsive-chemical activated luciferase gene expression (DR-CALUX) bioassay to three compost products (kitchen garbage compost, treated sludge compost, and poultry manure compost) and their organic waste materials was performed for the screening of dioxin-like compounds. Phased sample preparation was conducted for the bioassay to yield separate crude, acid-stable, and carbon column fractions. Chemical analyses were also conducted for polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polyaromatic hydrocarbons (PAHs). Their determined WHO-PCDD/PCDF/dl-PCB-TEQ values were compared to the DR-CALUX results expressed as CALUX-TEQ to ascertain their contributions to overall activity. Overall all three compost products were polluted to a low level by persistent PCDD/PCDF/dl-PCBs in a few pg/g WHO-TEQ concentration range. The organic crude fraction showed non-persistent CALUX-TEQ values 2-4 orders of magnitude higher than those of WHO-TEQ. For the acid-resistant fractions of all samples, persistent CALUX-TEQ values were 1-8-fold higher than WHO-PCDD/PCDF/dl-PCB-TEQ values. Both TEQs correlated well for this fraction, which confirms the availability of CALUX for estimation of the actual WHO-TEQ level of the samples using reflux method with 44% sulfuric acid/silica gel, although the compost and material samples examined in this study contained much lower levels of WHO-TEQ: less than 1 pg/g in almost all cases. Additional carbon column treatment enhanced the potency and efficacy of CALUX activity in the three compost samples, which showed 1.6-4.4 times higher values of CALUX-TEQ than those obtained for the acid-resistant fraction. Although further DR-CALUX data collection for compost samples will be necessary, DR-CALUX is useful as a rapid screening method for monitoring dioxin-like compounds in compost.     

Performance of bioreactor landfill with waste mined from a dumpsite

Emissions from landfills via leachate and gas are influenced by state and stability of the organic matter in the solid waste and the environmental conditions within the landfill. This paper describes a modified, ecologically sound waste treatment technique, where municipal solid waste is anaerobically treated in a lysimeter-scale landfill bioreactor with leachate recirculation to enhance organic degradation. The results demonstrate a substantial decrease in organic matter (BOD 99%, COD 88% and TOC 81%) and a clear decrease in nutrient concentrations especially ammonia (85%) over a period of 1 year with leachate recirculation.     

Assessment of relative accuracy in the determination of organic matter concentrations in aquatic systems

Accurate determinations of total (TOC), dissolved (DOC) and particulate (POC) organic carbon concentrations are critical for understanding the geochemical, environmental, and ecological roles of aquatic organic matter. Of particular significance for the drinking water industry, TOC measurements are the basis for compliance with US EPA regulations. The results of an interlaboratory comparison designed to identify problems associated with the determination of organic matter concentrations in drinking water supplies are presented. The study involved 31 laboratories and a variety of commercially available analytical instruments. All participating laboratories performed well on samples of potassium hydrogen phthalate (KHP), a compound commonly used as a standard in carbon analysis. However, problems associated with the oxidation of difficult to oxidize compounds, such as dodecylbenzene sulfonic acid and caffeine, were noted. Humic substances posed fewer problems for analysts. Particulate organic matter (POM) in the form of polystyrene beads, freeze-dried bacteria and pulverized leaf material were the most difficult for all analysts, with a wide range of performances reported. The POM results indicate that the methods surveyed in this study are inappropriate for the accurate determination of POC and TOC concentration. Finally, several analysts had difficulty in efficiently separating inorganic carbon from KHP solutions, thereby biasing DOC results.     

Investigation of 15-year-old municipal solid waste deposit profiles by means of FTIR spectroscopy and thermal analysis

Five profiles of a 15-year-old bank containing over three weeks composted municipal solid waste were characterized by means of different parameters habitually applied in waste management (loss on ignition, total organic carbon, total nitrogen, NH(4)-N, pH), and in addition by humic acid determination, FTIR spectroscopy and thermal analysis. Stabilization processes are revealed by humic acid contents. Over the 15 year period organic matter had developed in various ways. Highest humic acid contents were found at 0.5 m below the surface. Below 1.0-1.5 m anaerobic conditions dominated causing a strong decline of humic acid concentrations. Despite similar contents of organic matter at 0.5 m and at 3.0 m organic matter quality differed. These differences were verified by infrared spectroscopic investigations and thermal analyses (differential scanning calorimetry DSC). The spectral pattern of 15-year-old profile samples (municipal solid waste including the biogenic fraction) was compared to current municipal solid waste and abandoned landfill materials. Current municipal solid waste samples comprised different degradation stages from fresh materials to stabilized waste, suitable for landfilling according to Austrian standards. Municipal solid waste originating from abandoned landfills closed in the seventies represented stable material. Principal component analysis was performed to detect similarities and differences. It is evident that the profile samples constitute a particular group in between municipal solid waste and abandoned landfill material. Some differences can be attributed to the divergent composition of municipal solid waste in the eighties when the organic fraction was not separated. Otherwise, landfill materials from the seventies with the same composition regarding the organic fraction were deposited together with construction waste. Heat flow curves (DSC profiles) of municipal solid waste, representing different decomposition stages, illustrate the development of enthalpies and reveal the status of the profile samples. It is evident that mechanical-biological pretreatment leads to a faster stabilization of waste organic matter.     

Characterization and pollution potential assessment of Tunceli, Turkey municipal solid waste open dumping site leachates

Environmental monitoring of leachate quality from an open municipal solid waste dumping site in Tunceli, Turkey was studied in this research. The most commonly examined pollution parameters were determined on a seasonal basis. The annual average 5-day biological oxygen demand (BOD₅) and chemical oxygen demand (COD) values of station points were measured as 70 and 425 mg/L, respectively, and also the average BOD₅/COD ratio (a measure of biodegradability) was calculated as 0.20. The low ratio of biodegradability and slightly alkaline pH values in the leachate samples indicated that the site was characterized by methanogenic conditions. The mean ammonium-nitrogen (NH₄ ⁺-N) and corresponding phosphate (orthophosphate) values were assayed as 70 and 11 mg/L, respectively. The average solids content in the leachates was measured as 4,681 mg/L (total solids) and 144 mg/L (suspended solids). Very low concentrations of iron, manganese, copper, and zinc in the leachate samples were found and the concentration of cadmium was measured below detection limits. Excessive amount of nutrients and high organic and inorganic pollutant content in the leachates pose serious pollution potential to the environment. Since no drainage system or bio treatment exists in this open dumping site, high permeability of natural soil at the site and in the surrounding area and very fractured and crackled rocks under natural soil are indicators of high groundwater pollution potential in this site.     

地表水中TOC与COD换算关系研究

总有机碳(TOC)相对于化学需氧量(COD) 能够更全面地反映水体中有机物的污染程度,且TOC测定仪操作简单,数据准确。通过18个地表水水质自动监测站对水中有机污染物的COD与TOC监测数据的相关性研究,建立了TOC与COD之间的线性回归方程,为地表水的TOC监测代替COD监测提供了数据支持。     

Characterization of landfill leachates and studies on heavy metal removal

This study covers a thorough characterisation of landfill leachates emerging from a sanitary landfill area. The landfill leachates were obtained in the acidic stage of landfill stabilisation. Their organic content was high as reflected by the high BOD5 (5 day biological oxygen demand) and COD (chemical oxygen demand) values. They were also highly polluted in terms of the parameters TKN (total Kjeldahl nitrogen), NH4-N, alkalinity, hardness and heavy metals. Nickel was present in these wastewaters at a significant concentration. With regard to the high heavy metal content of these wastewaters, several physicochemical removal alternatives for the heavy metals Cu, Pb, Zn, Ni, Cd, Cr, Mn and Fe were tested using coagulation, flocculation, precipitation, base addition and aeration. Additionally, COD removal and ammonia stripping were examined. Co-precipitation with either alum or iron salts did not usually lead to significantly higher heavy metal removal than lime alone. The major methods leading to an effective heavy metal removal were aeration and lime addition. Nickel and cadmium seemed to be strongly complexed and were not removed by any method. Also lead removal proved to be difficult. The results are also discussed in terms of compliance with standards.     

Genotoxicity evaluation of water soil leachates by Ames test, comet assay, and preliminary Tradescantia micronucleus assay

Combining genotoxicity/mutagenicity tests and physico-chemical methodologies can be useful for determining the potential genotoxic contaminants in soil samples. The aim of our study was to evaluate the genotoxicity of soil by applying an integrated physico-chemical-biological approach. Soil samples were collected at six sampling points in a Slovenian industrial and agricultural region where contamination by heavy metals and sulphur dioxide (SO₂) are primarily caused by a nearby power plant. The in vitro alkaline version of the comet assay on water soil leachates was performed with Caco-2 and HepG2 cells. A parallel genotoxicity evaluation of the samples was performed by Ames test using Salmonella typhimurium and the Tradescantia micronucleus test. Pedological analyses, heavy metal content determination, and different physico-chemical analyses, were also performed utilizing standard methodology. Water leachates of soil samples were prepared according to standard methods. Since only a battery of biotests with prokaryotic and eukaryotic organisms or cells can accurately estimate the effects of (geno)toxicants in soil samples and water soil leachates, a combination of three bioassays, with cells or organisms belonging to different trophic levels, was used. Genotoxicity of all six water soil leachates was proven by the comet assay on both human cell lines, however no positive results were detected by bacterial assay, Ames test. The Tradescantia micronucleus assay showed increase in micronuclei formation for three samples. According to these results we can assume that the comet assay was the most sensitive assay, followed by the micronucleus test. The Ames test does not appear to be sensitive enough for water soil leachates genotoxicity evaluations where heavy metal contamination is anticipated.     

Prolonged toxicity characteristic leaching procedure for nickel and copper aluminates

The toxicity characteristic leaching procedure (TCLP) is a regulatory testing method widely employed to evaluate the environmental friendliness of waste materials. TCLP analysis provides a fast, easy and economical way to determine the mobility of waste pollutants under simulated landfill conditions. Recent studies on metal stabilization have reported the potential for nickel and copper aluminates to form in thermal treatment conditions, and suggested a more reliable method of stabilizing hazardous metals, particularly when products are to be reused. There is thus an urgent need for a convenient and effective method of quantifying metal leachability and identifying the metal leaching behavior of sparingly soluble materials. In this study, standard TCLP analysis was modified into a prolonged leaching experiment to investigate the leaching behavior of nickel and copper oxides (NiO and CuO) and their aluminates (NiAl(2)O(4), CuAl(2)O(4) and CuAlO(2)). The results demonstrate the difficulty of differentiating the leachability of highly insoluble phases, such as NiO and NiAl(2)O(4), using the standard TCLP. The prolonged TCLP method, however, confirmed NiAl(2)O(4) to have a lower degree of intrinsic leachability than NiO and that it could be expected to undergo congruent dissolution under landfill conditions. For the more soluble copper system, the aluminates were still found to possess a much lower degree of leachability, and their leaching behavior to follow an incongruent dissolution pattern. The results of this study prove prolonged TCLP analysis to be a convenient and effective way to evaluate the environmental friendliness of metal waste and to identify the leaching behavior of waste materials.     

Assessing the feasibility of wastewater recycling and treatment efficiency of wastewater treatment units

Wastewater reuse can significantly reduce environmental pollution and save the water sources. The study selected Cheng-Ching Lake water treatment plant in southern Taiwan to discuss the feasibility of wastewater recycling and treatment efficiency of wastewater treatment units. The treatment units of this plant include wastewater basin, sedimentation basin, sludge thickener and sludge dewatering facility. In this study, the treatment efficiency of SS and turbidity were 48.35–99.68% and 24.15–99.36%, respectively, showing the significant removal efficiency of the wastewater process. However, the removal efficiencies of NH₃–N, total organic carbon (TOC) and chemical oxygen demand (COD) are limited by wastewater treatment processes. Because NH₃–N, TOC and COD of the mixing supernatant and raw water are regulated raw water quality standards, supernatant reuse is feasible and workable during wastewater processes at this plant. Overall, analytical results indicated that supernatant reuse is feasible.     

Variation of total organic carbon content along the stream Harsit, Eastern Black Sea Basin, Turkey

The TOC in surface waters and wastewater is an important analytical parameter describing the total content of all organic substances containing carbon. In practice, the TOC originated from natural and anthropogenic sources, and even if it is not directly responsible for dangers on human health, its determination is important for any kind of water that is used by public. The aim of this study was to determine variation of total organic carbon (TOC) and total carbon (TC) content in the stream Harsit, which courses in Eastern Black Sea Region, Turkey. Sampling was fortnightly conducted in each of the four seasons between March 2009 and February 2010. A total of 230 water samples were collected from ten sampling stations along the main branch of the stream Harsit with 143 km of length. Obtained TOC values were evaluated and used to classify the water quality of stream Harsit, according to the Turkish Water Pollution Control Regulation (TWPCR). The annual average TOC content values for the stations were found between 2.33 and 6.97 mg/L. It was seen that the TOC content have increased along the streamcourse of Harsit until the fourth station, where reaches its maximum value. The TOC content, then, has decreased and the minimum value was observed in the eighth station. The results showed that, except in winter season, maximum TOC content observed in many of the water samples were above Class I water standard indicated in TWPCR, which classifies the water resources according to the different area of uses. It was also found that TOC has a small contribution to TC and the highest TOC content in stream waters were measured in Gumushane station where direct discharge of city wastewaters and solid waste dumping to the stream were observed.