Hazardous Waste Samples Research Articles

PROPOSITION OF THRESHOLD FOR WASTE CONTAMINATED WITH MERCURY (COMPOUNDS) IN APPLICATION OF THE MINAMATA CONVENTION ON MERCURY AND IMPACT ASSESSMENT

The Minamata Convention on Mercury is a global treaty to protect human health and the environment from the adverse effects of mercury. Environmentally sound management of waste is under discussion. This note proposes a threshold for waste of category c) Contaminated with mercury or mercury compounds to be disposed of (Article 11 of the Convention), using the Globally Harmonized System of classification and labelling of chemicals of the United Nations (GHS - UNEP 2017). Mercury and mercury compounds are classified as substances for the physical, health and environmental hazards categories. The thresholds of mercury and mercury compounds classifying a mixture as hazardous for the different hazard categories (physical, health, environmental) are “Presence”, >0.1% and >0.0025% (25 mg mercury/kg of waste) respectively. For impact assessment, this threshold is then compared with large data set of hazardous (793 data), potentially hazardous (depending on the concentration of hazardous substances) (55 data), as well as natural or non-polluted anthropized media (composts, sediments, agricultural soils) (21 784 data) from France. This demonstrates that 75% of the hazardous waste have higher total mercury concentration, that potentially hazardous waste samples have lower concentrations, and that all composts, agricultural soils and marine sediments and 99% of the fluvial sediments have lower concentrations. So, this threshold will not classify common industrial waste or natural media as requiring special treatment for safe disposal, but well a large part of industrial hazardous waste.

폐유 및 액상연료 공정 폐기물에서 무기물질류의 함량특성

국내 유해폐기물의 적정 관리를 위해 폐유 및 액상연료 공정에서 발생한 폐기물 중 규제 무기물질류의 배출특성을 조사하였다. 사업장은 올바로시스템에 등록된 폐기물 배출업체를 대상으로, 유럽폐기물 분류체계(EWC, European Waste Catalogue)의 폐유 및 액상연료 공정(EWC 13)과 유사한 폐기물 발생업체를 선정하였다. 조사대상 사업장 37 개 업체를 현지 방문하여 원료, 생산제품, 생산 공정, 폐기물의 종류 및 배출과정을 조사하고 생산 공정에서 배출되는 51 개의 폐기물을 채취하여 무기물질류 16 항목(Cd, Pb, Cu, Hg, As, CN, Cr, <TEX>$Cr^{6+}$</TEX>, Ba, Be, F, Ni, Sb, Se, V, Zn)에 대한 함량분석을 수행하였다. 분석결과, 모든 공정에서 발생된 폐기물에서 주로 Sb가 검출되었고, 6~419(평균 98) mg/kg의 농도 범위를 나타내었다. EWC 판정 절차를 통해 국내 폐유 및 액상연료 공정에서 발생된 폐기물을 판정한 결과, EWC 중분류 24공정 중 절대유해폐기물로 분류해서 관리해야할 공정은 16 개, 상대유해폐기물로 관리가 필요한 공정은 8 개로 판단되었다. 폐기물의 배출특성을 통해 유해물질 함유 자료를 확보하고 폐기물 목록에 대한 데이터베이스를 구축함으로써 유해폐기물의 안전처리를 통한 환경오염을 방지할 수 있을 것으로 기대된다. This study was performed to investigate the contents characteristics of hazardous oil wastes and wastes of liquid fuels from different industrial process. In order to establish a hazardous waste list, samples of various industrial discharge have been analyzed for 16 non-regulated inorganic hazardous substances (i.e., Cu, Pb, Cd, CN, Hg, As, T-Cr, <TEX>$Cr^{6+}$</TEX>, Sb, Ni, F, V, Ba, Zn, Be, Se). In more detail, hazardous waste samples including waste hydraulic oils, waste engine, gear and lubricating oils, waste insulating and heat transmission oils, bilge oils, oil/water separator contents processing were collected from 37 workplaces and analyzed. We observed that the most of the inorganic substances exceeded the proposed criteria in many samples. Especially the concentration of Sb in heat transmission oil, bilge oil and gear & lubricating oils were ranged from 6 to 419 mg/kg whereas the proposed criteria is 50 mg/kg. The assessment result of hazardous waste in Korea according to the EWC showed that the out of 24 processes, 16 belongs to absolute entry and 8 belongs to mirror entry. In conclusion, we expect the outcome of this study to align the classification system of hazardous waste management in South Korea with international legislations, and consequently contribute to reduce environmental pollution as well as health risks by toxic wastes.

Study on Suitability of Hazardous Wastes Entering the Landfill Directly

Abstract The physicochemical properties of eight hazardous waste samples (S1, S2, S3, S4, S5, S6, S7 and S8) obtained from Heilongjiang Province were analyzed to assess the suitability of landfill directly. The results showed that the wet content of eight samples was according with the landfill standards. However, some parameters of the samples S1, S2, S5 and S6 were not up to the standards. In addition, the Fe, Mn, Zn, Ni, Cr, and Be content in samples S1 and S5 exceeded the landfill standard limit. The sources of heavy metals were identified by analysing the correlation of the Zn, Mn and Ni concentration in different samples. The result showed that the correlation coefficient of the Zn, Mn and Ni concentration exhibited a significant level, which indicated that the metal Zn, Mn and Ni might originate the same source. The inorganic fluoride content in all samples did not exceed the landfill control standard, whereas the cyanide concentration was as 244.80∼2 692.76 times as the control limits except S1. In addition, benzene series were detected in some samples except S6 and S7, indicating that these samples needed pre-treatment before landfill.

국내 도료공정 발생 폐기물 중 미규제 중금속류의 배출특성

This study was performed to investigate the contents and leaching characteristics of hazardous wastes from the paint industry. In order to establish a hazardous waste list, samples from industrial discharge have been analyzed for 8 non-regulated inorganic hazardous substances (i.e., Sb, Ni, F, V, Ba, Zn, Be, Se). In more detail, hazardous waste samples from a total of 64 workplaces, e.g. manufacture, formulation, supply and use (MFSU) of coatings, adhesives, sealants and printing inks processing, have been chosen and analyzed. Contents and leaching tests for inorganic metal species in samples show that the non-regulated hazardous substances satisfy all the criteria, while quantitative analyses reveal that some samples of the discharged wastes exceeded the criteria proposed by NIER (National Instituted of Environmental Research). In conclusion, we expect the outcome of this study to align the classification system of hazardous waste management in South Korea with international legislations, and consequently contribute to reduce environmental pollution as well as health risks by toxic wastes.

Characterization of persistent-bioaccumulative-toxic (PBTs) substances in hazardous waste: Integration of chemical analysis and in vitro fish cells response

High-resolution gas chromatography mass spectrometry (HRGC/MS) is the standard method for analyzing dioxin, furan, and polybrominated retardants in hazardous waste. Methods based on biological interactions (ligand–receptor recognition) have begun only recently to be investigated in the context of environmental applications. We have compared dioxin, furan, and polybrominated diphenyl ethers toxicity levels by two analytical approaches: HRGC/MS analysis and a battery of in vitro bioassays with the fish cell line rainbow trout gonad cell line-2 (RTG-2), in nine (liquid and solid) hazardous waste samples. The battery assays included a cytotoxicity neutral red bioassay, a Kenacid blue protein content bioassay, an ethoxyresorufin O-deethylase bioassay, and a β-galactosidase bioassay. A dose-dependent stimulation of enzymatic activities was observed in four of the nine samples, associated to high levels of octachlorodibenzo-p-dioxin (OCDD) and/or polychlorinated biphenyls (PCB) 77 congener. The enzymatic values of the whole samples were higher than the extracts’ values, which indicated that there had to be other effective compounds in the waste samples that could be lost in the extraction-purification process. The outcome of both approaches makes the bioassay useful as a rough estimate for the synergistic or antagonistic effects of polychlorinated dibenzo-p-dioxins (PCDDs)/Fs and dl-PCBs in extracts from the samples, and it can provide preliminary information regarding the characterization procedure in ecological risk.

Analytical Problems Associated with the Analysis of Metals in a Simulated Hazardous Waste

Analysis of samples subject to physical and chemical interferences can greatly enhance the learning experience in instrumental analysis and environmental chemistry laboratories. This article describes a project-based experience in which students analyze simulated hazardous waste samples (carbonated beverages) for calcium by six techniques: (i) flame atomic absorption spectroscopy (FAAS) using external standard calibration, (ii) FAAS using external standard calibration with a releasing agent (Sr), (iii) FAAS using standard addition, (iv) FAAS using standard addition with a releasing agent (Sr), (v) ethylenediaminetetraacetic acid (EDTA) titration, and (vi) Ca-ion-specific electrode. Not surprisingly, students find that these different techniques yield conflicting results and their assignment is to explain their data in the format of a peer-reviewed journal article. Students report that this series of lab experiments is challenging and highly rewarding. Laboratory experiences such as this one should significantly improve the student's ability to analyze problematic samples and interpret experimental data.

Identification and Quantification of Organic Solvents in Flammable Hazardous Wastes by GC/FT-IR

A wide variety of organic solvents within flammable hazardous wastes were determined by GC/FT-IR using external calibration. The hazardous waste samples were prepared for analysis by dilution with hexane. The type of compounds analyzed included acetate esters, alcohols, aromatics, ethylene glycol ethers, chlorinated hydrocarbons, ketones, and other industrial solvents. The instrumental detection limits for the various compounds ranged from 4 to 240 μg/mL. Calibration curves were linear over one to two orders of magnitude and stable for several months. The percent relative standard deviation ranged from 0.9 to 10.0% and the percent bias was within ±23% for all analytes.

Closed-system, solid-phase extraction cleanup method for removal of normal paraffin hydrocarbon from samples prior to purge-and-trap volatile analysis

A novel approach has been developed to separate potential semivolatile interferences from volatile analytes prior to purge-and-trap analysis. This technique involves a closed system with solid-phase extraction which provides a simple, inexpensive method with minimal loss of volatile components. In addition, the separation method minimizes the potential adsorption of unwanted volatile species from the surrounding air during the cleanup procedure and reduces the radioactive level in actual tank waste samples. This cleanup method has been applied to radioactive, hazardous mixed waste samples containing normal paraffin hydrocarbon (NPH) from a Hanford single-shell tank. NPH, present at the percent level in actual tank wastes either as a native component or introduced as a hydrostatic fluid, interferes with the purge-and-trap gas chromatography/mass spectrometry (GC/MS) analysis of volatile components. Validation of the procedure was performed by analyzing blank spikes and actual, spiked single-shell tank waste samples. The NPH removal from actual waste samples and blank samples was better than 99%. This methodology could be easily extended to a sample matrix, such as water, sorbents, or soils, that contains excessive quantities of normal paraffin hydrocarbons. 9 refs., 8 figs., 4 tabs.

Distinguishing diphenylamine and N-nitrosodiphenylamine in hazardous waste samples by using high-performance liquid chromatography/thermospray/mass spectrometry

N-Nitrosodiphenylamine and diphenylamine in environmental samples cannot be easily distinguished and determined by conventional gas chromatography/mass spectrometry. By using a high-performance liquid chromatography/thermospray/mass spectrometry technique, the authors were able to directly distinguish these two compounds in a complex environmental matrix. Analytical results showed two distinct chromatographic peaks and distinct mass spectra of these two compounds. The unequivocal identification and measurement of one of the compounds in a contaminated soil sample from a hazardous waste site is demonstrated.

Environmental semivolatiles and nonvolatiles analysis by hyphenated spectral techniques.

Environmental sample extracts contain a variety of volatile and nonvolatile organic compounds exhibiting a range of polarities and concentrations. Although gas chromatography/mass spectrometry (GC/MS) is the method of choice thus far for such analyses, this technique used alone cannot adequately characterize the volatiles in such samples and is not amenable to environmental nonvolatiles. A more complete characterization of environmental and hazardous waste samples is required to assess the dangers posed to the nation's groundwater by hazardous waste dumps. Online spectral confirmation by directly linked GC/Fourier transform infrared (FTIR)/MS is shown to provide useful structural information on environmental volatiles in hazardous wastes, even when the analyte's spectrum is not in either spectral database. This information can lead to biological-hazard estimation. The diffuse reflectance Fourier transform infrared (DRIFT) technique, used in conjunction with thermospray MS or fast atom bombardment (FAB) MS, provides confirmed identifications or confirmed compound class assignments of organic nonvolatiles in solid wastes. This is believed to be the first report of spectral confirmation (identification or functionality) of organic volatiles and nonvolatiles in environmental samples.

Use of the microscreen phage-induction assay to assess the genotoxicity of 14 hazardous industrial wastes.

The Microscreen phage-induction assay, which quantitatively measures the induction of prophage lambda in Escherichia coli WP2s(lambda), was used to test 14 crude (unfractionated) hazardous industrial waste samples for genotoxic activity in the presence and absence of metabolic activation. Eleven of the 14 wastes induced prophage, and induction was observed at concentrations as low as 0.4 pg per ml. Comparisons between the ability of these waste samples to induce prophage and their mutagenicity in the Salmonella reverse mutation assay indicate that the phage-induction assay detected genotoxic activity in all but one of the wastes that were mutagenic in Salmonella. Moreover, the Microscreen assay detected as genotoxic five additional wastes that were not detected in the Salmonella assay. The applicability of the Microscreen phage-induction assay for screening hazardous wastes for genotoxic activity is discussed, as are some of the problems associated with screening highly toxic wastes containing toxic volatile compounds.

Mutagenicity in Salmonella of hazardous wastes and urine from rats fed these wastes

15 hazardous industrial waste samples were evaluated for mutagenicity in the Salmonella plate-incorporation assay using strains TA98 and TA100 in the presence and absence of Aroclor 1254-induced rat liver S9. Dichloromethane/methanol extracts of the crude wastes were also evaluated. 7 of the crude wastes were mutagenic, but only 2 of the extracts of these 7 wastes were mutagenic; extracts of 2 additional wastes also were mutagenic. In addition, 10 of the crude wastes were administered by gavage to F-344 rats, and 24-h urine samples were collected. Of the 10 raw urines evaluated, 3 were mutagenic in strain TA98 in the presence of S9 and β-glucuronidase. The 3 crude wastes that produced these 3 mutagenic urines were, themselves, mutagenic. Adequate volumes of 6 of the 10 raw urines were available for extraction/concentration. These 6 urines were incubated with β-glucuronidase and eluted through Sep-Pak® C 18 columns; the methanol eluates of 3 of the urines were mutagenic, and these were the same 3 whose raw urines also were mutagenic. In general, the C 18/methanol extraction procedure reduced the cytotoxicity and increased the mutagenic potency of the urines. To our knowledge, this is the first report of the mutagenicity of urine from rodents exposed to hazardous wastes. Based on the present results, the use of only strain TA98 in the presence of S9 might be adequate for general screening of hazardous wastes or waste extracts for genotoxicity. The urinary mutagenesis assay does not appear to be a useful adjunct to the Salmonella assay for screening hazardous wastes. The problems associated with chemically fractionating diverse types of hazardous wastes for bioassay are also discussed.

Qualitative screening of hazardous waste drum mixtures

Two automated infrared analysis techniques were reviewed as screening methods for unknown organic compounds in hazardous waste samples. The first method involves forward searching of spectra through a spectral library. The second method uses an automated artificial intelligence interpretation program named PAWMI. These two Fourier-transform infrared techniques were used on 11 hazardous waste samples that had been previously analyzed by gas chromatography/mass spectroscopy (GC/MS). The results of the forward searching showed that this method can be useful when the unknowns are relatively pure compounds and can be used to identify nonchromatographable components of mixtures. The PAWMI method demonstrated good success for those components of the waste present both in the program training set and in the samples at concentrations of > 1%. This method should be used for on-site analysis of hazardous waste samples to identify major constituents or organic chemical mixtures in conjunction with compatibility testing and/or GC/MS analyses. 35 references, 5 figures, 5 tables.