A Comprehensive Methodology for Assessing the Hazardousness of Waste Categorized in the European Union Legislation as “Mirror Entries”—Case Studies
Abstract
:1. Introduction
2. Methodology for Assessing Hazardous “Mirror Entry” Waste
- (a)
- The technological process of waste production, i.e., identify the technological process and the physical-chemical treatments applied to the process flow (if applicable).
- (b)
- The raw materials, i.e., prepare an inventory of the raw materials that enter the technological process and of the substances used in different stages of the technological process, including their balance sheets.
- (c)
- The material safety data sheets (MSDSs), i.e., use the MSDSs of the materials to identify the component substances and related concentrations (if applicable).
- (d)
- Information regarding the appearance of the waste, i.e., obtain information on the state of aggregation, color, estimated humidity, smell, and with or without petroleum product content.
- (e)
- The purpose of assessing the dangerousness and classification of the waste, i.e., depending on the method of subsequent management, simultaneously with the assessment of the dangerousness, determine other characteristics/parameters of the waste that can influence the final destination. This step is not mandatory, but it supports the producer/owner of the waste by providing additional helpful information. For example, in the case of waste that is managed through disposal in a waste deposit, it is necessary to carry out a leaching test to establish the type of waste deposit (i.e., inert, non-hazardous, or hazardous). Also, in the case of waste that is managed through energy recovery, it is essential to determine the calorific value, ash content, volatile substances, and other useful parameters, in addition to the potentially dangerous compounds in the waste.
2.1. Acid/Alkaline Reserve
2.2. Determining the Concentrations of Pollutants: Calculation Formulas
- (a)
- Determination of the concentrations of hazardous substances based on the physical-chemical indicators
- (b)
- Determination of the concentrations of hazardous substances in the waste based on MSDSs and the information provided by the waste producer
- -
- Weight of sludge generated in a month X (tonne);
- -
- Sludge humidity W (%);
- -
- The volume of wastewater treated in one month Y (sqm);
- -
- Mass of dangerous substance (kg) used in the technological process in a month related to the concentration indicated in the safety data sheet.
3. Materials and Methods
3.1. Case Studies
3.2. Test Leaching
3.3. Techniques and Methods of Analysis
4. Results
5. Discussion
6. Conclusions
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Indicator | Standard Method | Techniques/Equipment |
---|---|---|
pH | EN ISO 10390:2022 [38] | pH meter |
Total moisture | SR EN 15934:2012 [39] SR EN 15002:2015 [40] | Gravimetry |
Chloride | STAS 7184/7-87 [41] | Volumetry |
Sulphates | SR ISO 11048:1999 [42] | Gravimetry Gravimetry |
Carbonates | STAS 7184/7-87 [43] | |
Total nitrogen | SR EN 16168:2013 [44] | CHNS-O Analyzer EA 1112 |
Total organic carbon (TOC) | SR EN: 15936:2022 [45] | Carbon/Sulfur Analyzer 580A |
Silicon and major elements (total iron, calcium, magnesium, potassium, zinc) | SR EN 15309:2007 [46] | X-ray fluorescence (XRF) |
Heavy metals minor elements (manganese, cadmium, total chromium, mercury, copper, nickel, arsenic, titanium, vanadium, antimony, selenium, barium) | SR EN 16171:2017 [47] SR EN 16173:2013 [48] SR EN 54321:2021 [49] | Mass spectrometry with inductively coupled plasma (ICP-MS), Agilent 7900 |
Dissolved organic carbon (DOC) | SR EN 1484:2001 [50] | Combustion and IR detection |
Indicators | W1 | W2 | W3 | |||
---|---|---|---|---|---|---|
mg/kg d.m. | % | mg/kg d.m. | % | mg/kg d.m. | % | |
Na | 15.38 | 0.0013 | 5086 | 0.47 | -* | -* |
Ca | 83,000 | 6.83 | 2208 | 0.20 | 50,870 | 4.79 |
Si | 52,380 | 4.31 | 24,1916 | 22.42 | -* | -* |
K | -* | -* | 1592 | 0.15 | -* | -* |
Mg | -* | -* | 1367 | 0.13 | 12,410 | 1.17 |
Mn | -* | -* | 5.07 | 4.7 × 10−4 | 21,180 | 1.99 |
Pb | 0.65 | 5.4 × 10−5 | 15.5 | 0.0014 | 9870 | 0.93 |
As | -* | -* | -* | -* | <0.05 | - |
Co | -* | -* | 15.6 | 0.0015 | -* | -* |
Total iron | 4300 | 0.35 | 156 | 0.015 | 395,500 | 37.2 |
Cd | 0.10 | 8.2 × 10−6 | -* | -* | -* | -* |
Total chromium | 0.16 | 1.3 × 10−5 | 8.63 | 8 × 10−4 | 770 | 0.072 |
Cu | -* | -* | 65.9 | 0.0061 | 830 | 0.078 |
Ni | 0.45 | 3.70 × 10−5 | -* | -* | -* | -* |
Zn | 0.39 | 3.2 × 10−5 | -* | -* | 345,000 | 32.5 |
V | <0.15 | - | -* | -* | <0.15 | - |
Ba | -* | -* | -* | -* | 182 | 0.017 |
B | -* | -* | 128.1 | 0.012 | -* | -* |
Al | 16,200 | 1.33 | 522 | 0.048 | 3820 | 0.36 |
Chloride | 493 | 0.041 | -* | -* | 17,090 | 1.61 |
Total nitrogen | -* | -* | -* | -* | -* | 0.01 |
Total organic carbon (TOC) | -* | 0.39 | -* | 0.32 | -* | -* |
Carbonates | -* | 23.1 | -* | 1.5 | -* | -* |
Sulphate | 310 | 0.025 | 545 | 0.05 | 5682 | 0.54 |
Indicators | Leachate Test | Order 2005/95 (MAV) | |||||
---|---|---|---|---|---|---|---|
Units | LW1 | LW2 | LW3 | (I) | (NHA) | (HA) | |
Arsenic | mg/kg d.m. | <0.07 | <0.07 | <0.07 | 0.5 | 2 | 25 |
Barium | mg/kg d.m. | 0.43 | 0.80 | 3.76 | 20 | 100 | 300 |
Cadmium | mg/kg d.m. | <0.05 | <0.05 | <0.05 | 0.04 | 1 | 5 |
Total chromium | mg/kg d.m. | <0.05 | <0.05 | 0.23 | 0.5 | 10 | 70 |
Copper | mg/kg d.m. | <0.01 | 0.19 | 1.88 | 2 | 50 | 100 |
Mercury | mg/kg d.m. | <0.05 | <0.05 | <0.05 | 0.01 | 0.2 | 2 |
Molybdenum | mg/kg d.m. | <0.10 | 0.11 | 0.26 | 0.5 | 10 | 30 |
Nickel | mg/kg d.m. | <0.03 | 0.05 | 0.82 | 0.4 | 10 | 40 |
Lead | mg/kg d.m. | <0.07 | 0.21 | 12.8 | 0.5 | 10 | 50 |
Antimony | mg/kg d.m. | <0.50 | <0.50 | <0.50 | 0.06 | 0.7 | 5 |
Selenium | mg/kg d.m. | <0.13 | <0.13 | <0.13 | 0.1 | 0.5 | 7 |
Zinc | mg/kg d.m. | <0.03 | 0.54 | 568 | 4 | 50 | 200 |
Chloride | mg/kg d.m. | 229 | 15.8 | 8542 | 800 | 15,000 | 25,000 |
Fluoride | mg/kg d.m. | <0.05 | <0.05 | 5.96 | 10 | 150 | 500 |
Sulphate | mg/kg d.m. | 111 | 98 | 3478 | 1000 | 20,000 | 50,000 |
Phenol index | mg/kg d.m. | <0.20 | <0.20 | <0.20 | 1 | -* | -* |
Dissolved organic carbon (DOC) | mg/kg d.m. | 630 | 527 | 128 | 500 | 800 | 1000 |
Total dissolved solids (TDS) | mg/kg d.m. | 5060 | 7012 | 33,460 | 4000 | 60,000 | 100,000 |
Hazardous Property | Hazardous Phrase | Analyzed Indicator/ Associated Compound | Concentration of the Associated Compound (%) | Concentration Limit (%) Regulation EU 2014/1357 |
---|---|---|---|---|
HP4 | H318 | Ca/CaO | 9.56 | 10 |
H315, H319 | Ca/CaO | 9.56 | 20 | |
HP5 | H335 | Fe/FeO(OH) | 0.56 | 20 |
Ca/CaO | 9.56 | 20 |
Hazardous Property | Hazardous Phrase | Analyzed Indicator/ Associated Compound | Concentration of the Associated Compound (%) | Concentration Limit (%) Regulation EU 2014/1357 |
---|---|---|---|---|
HP4 | H314 (skin cor. 1A) | NaOH | 0.82 | |
Total | 0.82 | 1 | ||
H318 | NaOH | 0.82 | ||
Ca/Ca(OH)2 | 0.38 | |||
Al/Al2O5Si | 0.15 | |||
Cu/CuSO4x5H2O | 0.015 | |||
Total | -* | 10 | ||
H315, H319 | Na/Na2CO3x10H2O | 2.93 | ||
Fe/Fe3O4 | 0.02 | |||
Mg/Mg3(Si4O10)(OH)2 | 0.66 | |||
K/KOH | 0.21 | |||
TOC/C3H9NO2 | 0.809 | |||
Total | 2.93 | 20 | ||
HP5 | H335 | Na2SiO3 | 1.25 | 20 |
Mg/Mg3(Si4O10)(OH)2 | 0.66 | 20 | ||
TOC/C2H7NO | 0.813 | 20 | ||
Fe/Fe3O4 | 0.02 | 20 | ||
HP6 | H302 | Cu/CuSO4x5H2O | 0.015 | |
K/KOH | 0.21 | |||
TOC/C2H7NO | 0.813 | |||
Total | -* | 25 | ||
H332 | Mg/Mg3(Si4O10)(OH)2 | 0.66 | ||
TOC/C2H7NO | 0.813 | |||
Total | -* | 22.5 | ||
H312 | TOC/C2H7NO | 0.813 | 55 | |
Total | -* | |||
HP8 | H314 (skin cor. 1B) | Na2SiO3 | 1.25 | 5 |
KOH | 0.21 | |||
Total | 1.46 | |||
HP10 | H360 | B/H3BO3 | 0.017 | 0.3 |
B/Na2(B4O5(OH)4)*8H2O | 0.114 | 0.3 |
Hazardous Property | Hazardous Phrase | Analyzed Indicator/ Associated Compound | Concentration of the Associated Compound (%) | Concentration Limit (%) Regulation EU 2014/1357 |
---|---|---|---|---|
HP4 | H315, H319 | Fe/Fe2O3 | 53.26 | |
Cr/Cr2O3 * | 0.11 | |||
Cu/CuO * | 0.09 | |||
Mn/MnO | 2.58 | |||
Ca/CaO | 6.70 | |||
Al/Al2O3 * | 0.68 | |||
Mg/MgO | 1.94 | |||
Total * | 64.48 | 20 | ||
HP5 | H335 | Zn/ZnO | 40.44 | 20 |
Mg/MgO | 2.41 | 20 | ||
Mn/MnO | 2.58 | 20 | ||
Al/Al2O3 | 0.68 | 20 | ||
Cu/CuO | 0.09 | 20 | ||
HP6 | H332 | Mg/MgO | 2.41 | |
Pb/PbO | 1 | |||
Zn/ZnO | 40.44 | |||
Total | 43.85 | 22.5 | ||
HP10 | H360 | Pb/PbO | 1 | 0.3 |
Total | 1 | |||
HP11 | H341 | Cu/CuO | 0.09 | 1 |
Pb/PbO | 1 | 1 |
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Kim, L.; Cuciureanu, A.; Pascu, L.F.; Tache, O.C.; Catrina, G.A. A Comprehensive Methodology for Assessing the Hazardousness of Waste Categorized in the European Union Legislation as “Mirror Entries”—Case Studies. Environments 2023, 10, 183. https://doi.org/10.3390/environments10100183
Kim L, Cuciureanu A, Pascu LF, Tache OC, Catrina GA. A Comprehensive Methodology for Assessing the Hazardousness of Waste Categorized in the European Union Legislation as “Mirror Entries”—Case Studies. Environments. 2023; 10(10):183. https://doi.org/10.3390/environments10100183
Chicago/Turabian StyleKim, Lidia, Adriana Cuciureanu, Luoana Florentina Pascu, Oana Cătălina Tache (Țăpurică), and Gina Alina Catrina (Trăistaru). 2023. "A Comprehensive Methodology for Assessing the Hazardousness of Waste Categorized in the European Union Legislation as “Mirror Entries”—Case Studies" Environments 10, no. 10: 183. https://doi.org/10.3390/environments10100183
APA StyleKim, L., Cuciureanu, A., Pascu, L. F., Tache, O. C., & Catrina, G. A. (2023). A Comprehensive Methodology for Assessing the Hazardousness of Waste Categorized in the European Union Legislation as “Mirror Entries”—Case Studies. Environments, 10(10), 183. https://doi.org/10.3390/environments10100183