Effects of organic ligands and pH on the leaching of copper from brake wear debris in model environmental solutions

Copper leaching from a disc brake wear debris sample was examined in a variety of aqueous solutions to simulate potential leaching processes during rain events and in surface waters. Synthetic rainwater leached 40% of the total copper present in the brake wear debris into solution after 18 h in batch reactors, which was approximately three times more copper than that extracted by the US Environmental Protection Agency's Synthetic Precipitation Leaching Procedure. Formate and acetate were responsible for the enhanced copper leaching, as demonstrated by higher average amounts of leached copper in synthetic rainwater with- versus without the organic acids (40 versus 31% recovery). This observation suggests leaching tests that do not incorporate the appropriate types and concentrations of organic ligands present in rainwater will likely underestimate copper mobilization from brake wear debris during rain events. Leaching of copper from the brake wear debris ranged from 23 to 40% in solutions containing 3 to 15 mg C L(-1) dissolved humic substances, and was higher still in solutions containing relatively high concentrations of the synthetic metal chelating agent ethylenediaminetetraacetic acid. Static pH tests demonstrated that copper leaching from brake wear debris is highly pH dependent, with more leaching occurring at lower solution pH values. Leaching rate studies revealed that equilibrium generally was not attained within 48 h in the model solutions, indicating that additional copper can be expected to be released in environments where brake wear debris is exposed to long-term leaching processes.     

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.     

TCLP法对天津市农田重金属生态风险评价

TCLP法是用缓冲剂提取重金属的一种方法,该法评价重金属生态风险在美国已开展多年。利用TCLP法对天津市某农田土壤重金属进行生态风险评价,结果表明,在采集的23个样品中有效态铜、铅、锌、镉的含量范围为1.13~5.26、2.11~5.22、2.60~30.6、1.09×10-3~77.9×10-3mg/kg,普遍低于铜、铅、锌、镉在土壤中的总量(22.1~66.8、21.2~50.6、56.8~445、0.04~0.20 mg/kg)。镉的TCLP有效态与总量的差别最大。锌、铅存在轻微污染,污染率分别为21.7%、4.3%。     

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.     

水中总氮测定方法存在问题的研究及改进

碱性过硫酸钾消解紫外分光光度法测定水中总氮采用的消解器皿是玻璃比色管,易造成空白偏高、结果偏低等问题。采用双圆柱状的消解杯对水样进行消解。结果表明,消解杯消解水中总氮,线性相关系数均大于0.999,检出限为0.05 mg/L,相对标准偏差小于5%,相对误差为0.88%~1.00%;改进后的消解器皿具有较好的精密度和准确度,能够更加准确测定水中总氮的含量。     

Leaching potential of silver from nanosilver-treated textile products

The use of nanosilver as an antibacterial agent for various products has increased, especially so, in textiles. This study aims to investigate the potential of Ag to leach from commercial products which contain nano-Ag by using the toxicity characteristic leaching procedure (TCLP) test in accordance with USEPA method 1311. Eight nano-Ag products were purchased from the market. Only those products that are likely to be disposed of in a landfill after end use were selected. Nano-Ag fabrics of different concentrations were also prepared at the laboratory scale, and the TCLP test was performed on them as well. The current study assumes that the new products were discarded without use. The Ag content was quantified by inductively coupled plasma–mass spectroscopy (ICP-MS) and ranged from 0.95 to 2.82 μg/g of the product in the commercial products and from 1.49 to 350 μg/g of the product in the lab-prepared fabrics. In the TCLP test results, Ag concentrations ranged from 4.3 to 64.9 μg/L in the commercial products and from 28.9 to 28,381 μg/L in the lab-prepared fabrics. The results also indicate that the amount of Ag released depends on the type of the fabrics. Additionally, the size of the nano-Ag released in percentage is different for each prepared fabric. This study can help in understanding the amount of Ag released during the disposal phase of a product in a landfill.     

Leaching Characteristics of Heavy Metals and As from Two Urban Roadside Soils

The leaching tests, including the Toxicity Characteristic Leaching Procedure (TCLP), EDTA extraction and BCR sequential extractions before and after EDTA treatments, were performed on two specific soils to elucidate heavy metal-associated mineral fractions and general leachability. The TCLP illustrated the low leachability of heavy metals in soils from two sites. EDTA is a strong chelator and therefore had higher extraction efficiency compared to that of TCLP. The lower extraction percentages by EDTA for As and Sb were found compared to the other heavy metals derived from anthropogenic sources. Sequential extractions showed that the importance of acid-extractable, organically-bound and Fe–Mn oxide fractions was identified for anthropogenic heavy metals with the exception of As and Ni while the importance of residual fraction was identified for endogenous metals. Changes in sequential fractions of heavy metals after leaching with EDTA are very complex and it is difficult to generalize on which fraction was more mobile than the others. These combined results are helpful in elucidating the association of heavy metals to soil fractions and the mobility characteristics of heavy metals under certain environmental conditions.     

垃圾渗滤液中微塑料分析的消解方法评价

微塑料（MPs）是近年来国内外关注度极高的新兴污染物,建立实际环境样品中MPs的分析方法是开展相关研究的基础。对于复杂污水样品而言,样品的消解过程至关重要,将极大地影响MPs的准确分析。选择垃圾渗滤液为典型复杂污水样品,采用样品浊度和色度变化、残余悬浮固体量、MPs在颗粒物中的占比为评价指标,对盐酸消解、30%过氧化氢消解及芬顿试剂消解3种常用消解方法的消解效果进行了比较。结果表明,30%过氧化氢对垃圾渗滤液样品的消解效果最佳,MPs在全部颗粒物中的占比达63.7%,极大地缩减了后续MPs定性分析的时间,降低了分析难度,且对渗滤液中MPs的回收率也高达（103±3）%。在此基础上,讨论了消解效果与过氧化氢投加量/样品浊度（V_H2O2/T₁）的关系。当V_H2O2/T₁为0.15~0.20 mL/NTU时,样品残余悬浮固体量最低,消解效果最佳。     

Leaching Characteristics of Fly Ash from Thermal Power Plants of Soma and Tunçbilek, Turkey

Use of lignite in power generation has led to increasing environmental problems associated not only with gaseous emissions but also with the disposal of ash residues. In particular, use of low quality coal with high ash content results in huge quantities of fly ash to be disposed of. The main problem related to fly ash disposal is the heavy metal content of the residue. In this regard, experimental results of numerous studies indicate that toxic trace metals may leach when fly ash contacts water. In this study, fly ash samples obtained from thermal power plants, namely Soma and Tunçbilek, located at the west part of Turkey, were subjected to toxicity tests such as European Committee for standardization (CEN) and toxicity characteristic leaching (TCLP) procedures of the U.S. Environmental Protection Agency (U.S. EPA). The geochemical composition of the tested ash samples from the power plant show variations depending on the coal burned in the plants. Furthermore, the CEN and TCLP extraction results showed variations such that the ash samples were classified as `toxic waste' based on TCLP result whereas they were classified as `non-toxic' wastes based on CEN results, indicating test results are pH dependent.     

程序控温石墨消解-原子荧光法测定土壤中总砷

采用程序控温石墨全自动消解仪消解土壤样品，原子荧光光谱法测定总砷。通过试验确定原子荧光光度计的最佳工作条件，使得该方法在2.00μg／L ～20.0μg／L 范围内线性良好，检出限为0.025 mg／kg，加标回收率在96.0％～10^5％之间，RSD为1.9％～3.3％。用该方法与国标法同时测定土壤标准样品和实际样品，结果无显著差异。     

Assessment of metal contamination using X-ray fluorescence spectrometry and the toxicity characteristic leaching procedure (TCLP) during remediation of a waste disposal site in Antarctica

The remediation of the Thala Valley landfill, Casey Station, East Antarctica, is part of efforts to clean-up contaminated sites associated with the Australian Antarctic Program. These sites, ranging from abandoned rubbish dumps to fuel spills, are contaminated principally with metals and petroleum hydrocarbons. Remediation success depends on accurate, cost-effective and timely--fit-for-purpose--chemical analysis of soil and water samples from the site, which is required to guide excavation, the in situ or off-site treatment and disposal of contaminated material, and to validate satisfactory remediation. Owing to the remote location of Antarctica, it is necessary to carry out chemical analyses on-site. Waste and soil contaminated with Pb, Zn, Cd, and Cu were excavated from Thala Valley for removal to Australia, treatment and disposal. Analysis of total metal concentrations in soil was performed at Casey Station with a transportable energy dispersive X-ray fluorescence (EDXRF) spectrometer. Soil samples were prepared using a simple size-fractionation method to expedite sample throughput. A method for assessing contaminant mobility in solid waste (toxicity characteristic leaching procedure, TCLP) was also used to characterise soil. Although this was more labour-intensive and time-consuming than the total metals analysis, it was of great utility because leachable metals were often significant determinants in the assessment of contaminated soil. The combined data helped managers during remediation, directing excavation and allowing waste to be classified for treatment and disposal before its return to Australia.     

Monitoring of heavy metal levels in roadside dusts of Thessaloniki, Greece in relation to motor vehicle traffic density and flow

In recent years, the level of heavy metal pollution in urban areas has been of considerable concern. The principal source has been attributed to the motor vehicle and increasing inner city congestion, which has lead to a change and enlargement of transport stop-start zones. These areas of high traffic density are associated with an increased release of heavy metals into the adjacent residential or commercial areas. Seventy-five roadside dust samples were collected throughout the inner city and by-pass motorway areas of Thessaloniki, Northern Greece. Samples were taken from arterial, major and minor roads, as well as the ring road, to compare and contrast the levels of heavy metals, namely Cu, Zn, Cd, Mn and Pb. Flame Atomic Absorption Spectroscopy (FAAS) was developed to quantitatively determine concentrations of both total element and geochemical fractionation, within the two dust particulate fraction sizes <75 microm and 75-125 microm. Acid digestion using Aqua Regia (3:1 conc. HCl:HNO(3)) was employed for the total elemental analysis, a method that was validated through the use of certified reference materials (CRM). Fractionation studies involved a three-step sequential extraction method performed on five selected samples (representatives of high, mid and low total elemental concentrations). The resultant solutions were analysed for lead and zinc levels to ascertain fractionation throughout the different geochemical fractions, thus assessing bioavailability.It was found that congestion/stop-start traffic patterns did influence and have led to increased levels of heavy metal deposition along inner city roads compared to levels observed on the new relief ring road. Dust particulate fraction sizes were only found to show statistically significant differences in cadmium and manganese, at the probability P < 0.001 or 99.9% confidence limit. Both Cd and Mn showed higher total levels in the smaller fraction sizes (<75 microm), implying that their major release source is exhaust emissions. There were no significant differences in the other elements, at the P > 0.05 or 95% confidence limit. Road type was seen to have little affect on cadmium and manganese, though lead, copper and zinc were all found to show higher levels on the inner city routes. This can be related back to the wear-and-tear of vehicle components as a result of the stop-start traffic patterns (brake pads etc). Both Pb and Zn have shown to be in chemical forms that are bio available to ecosystems.     

Total petroleum hydrocarbons and trace heavy metals in roadside soils along the Lagos–Badagry expressway, Nigeria

This study reports the level of total petroleum hydrocarbons (TPH) and trace heavy metals (lead, copper, and cadmium) in soil samples collected randomly from Iyana–Iba garage, Lagos State University bus stop, Adeniran Ogunsanya College of Education bus stop, and a control site off Lusada–Atan road, near Crawford University, Igbesa, Ogun state. TPH was estimated gravimetrically after Soxhlet extraction and column clean up, while soil metals were determined by atomic absorption spectrometry using mineral acid digestion. For TPH, the sites have mean values of 19.43 ± 1.27, 16.11 ± 1.85, and 11.43 ± 4.33 mg/g with a control mean value of 0.33 ± 0.16 mg/g. For trace heavy metals, cadmium was not detected. However, the mean levels of lead are 4.24 ± 3.10, 3.72 ± 0.60, and 3.70 ± 1.32 μg/g, respectively, whereas mean copper concentrations are 20.63 ± 9.02, 19.35 ± 3.61, and 16.76 ± 3.02 μg/g in all sites, respectively, compared to the control mean of 0.25 ± 0.13 and 5.99 ± 1.23 μg/g for lead and copper, respectively. Sites studied have higher levels of TPH and metals compared to the control soil samples. This is indicated by a statistically significant difference found between the concentration of analyzed elements in soils collected along Lagos–Badagry expressway and the control site.     

The relationship between whole effluent toxicity (WET) and chemical-based effluent quality assessment in Vojvodina (Serbia)

The relationship between whole effluent toxicity (WET) and chemical-based effluent quality assessment across a range of effluent types was examined for the first time in Serbia. WET was determined by Daphnia magna acute tests, while chemical-based toxicity was taken as theoretical for concentrations of priority chemicals and effluent quality assessment based on the valid Serbian regulations. A poor correlation was found between WET and chemical-based effluent quality assessment: positive toxicity tests were found, in general, in cases where samples satisfied the requirements of mandatory effluent monitoring. Statistically insignificant correlation between the predicted and observed toxicity indicated that the presence of priority substances accounted to the overall toxicity only to a certain degree, most probably due to a rather short list of priority pollutants regularly analysed in effluents. Current monitoring requirements neglect hazards that derive from potentially present toxicants and unpredictable toxicity of complex mixtures, which led to poor correlation between the WET and chemical-based results in this study.     

Whole Effluent Toxicity (WET) Tests on Wastewater Treatment Plants with Daphnia magna and Selenastrum capricornutum

Whole effluent toxicity (WET) tests, with Daphnia magna and Selenastrum capricornutum, were introduced to evaluate the biological toxicities of effluents from the wastewater treatment plants (WWTPs) in Korea. In WET tests of WWTPs effluents, 33.3% (33/99) for D. magna and 92.6% (75/81) for S. capricornutum revealed greater than 1 toxic unit (TU), even though all the treatment plants investigated were operating in compliance with the regulations, as assessed using conventional monitoring methods (i.e., BOD and total concentration of N or P, etc). There were only minor differences in toxicities according to the types of influents (municipal and agro-industrial) in all treatment plants. However, the effluents treated by an activated sludge treatment process were found to exhibit significantly lower toxicity than those treated by rotating biological contactor (RBC) and extended aeration processes. The seasonal variations in the toxicity were lower in the summer compared to winter, which may have been due to the rainfall received to the sewage intake system during the former period. The impact of WET on river water was also investigated based on the discharge volume. At sites A and B, the total impact of toxicity to stream and river waters was observed to be 70.9% and 90.4% for D. magna and S. capricornutum, respectively. The other four small treatment plants (sites F, G, H and I), with relative discharging volumes between 0.001 and 0.002, contribute less than 1% to the total toxicity.     

海洋沉积物中多种重金属的X射线荧光分析法

建立了海洋沉积物中包括砷、铜、铅、锌、镍和总铬在内的多种重金属X射线荧光分析法,测量不需要任何消解前处理过程,可在约1h内测量1个样品中的50余种元素,用该方法分析了8个海洋沉积物标准样品,还与原子荧光光谱法或原子吸收分光光度法比对分析了2个实际样品,结果表明,该方法可信度较高,且具有快速、简便、高效等特点,是一种非破坏性分析方法。     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

微波消解ICP-MS法同时测定大气颗粒物中多种痕量元素

采用微波消解电感耦合等离子体质谱法同时测定大气颗粒物中13种元素,选择硝酸体系消解20 min,硝酸加入体积为8 mL。Cu、Ni、Cr、Pb、Al、Mg、Mn、Ca在0μg/L～100μg/L,Ag、Ba、Co、Cd、Sn在0μg/L～5.00μg/L范围内线性良好,除Al、Mg、Ca检出限较高外,其他10种元素的检出限为0.07 ng/m3～1.82 ng/m3(按采样体积0.688 m3、定容体积50 mL计),滤膜样品平行测定3次的RSD≤1.2%,加标回收率在92%～108%之间。     

Trace element concentration and speciation in selected urban soils in New York City

A long history of urbanization and industrialization has affected trace elements in New York City (NYC) soils. Selected NYC pedons were analyzed by aqua regia microwave digestion and sequential chemical extraction as follows: water soluble (WS); exchangeable (EX); specifically sorbed/carbonate bound (SS/CAR); oxide-bound (OX); organic/sulfide bound (OM/S). Soils showed a range in properties (e.g., pH 3.9 to 7.4). Sum of total extractable (SUM_TE) trace elements was higher in NYC parks compared to Bronx River watershed sites. NYC surface horizons showed higher total extractable (TE) levels compared to US non-anthropogenic soils. TE levels increased over 10 year in some of the relatively undisturbed and mostly wooded park sites. Surface horizons of park sites with long-term anthropogenic inputs showed elevated TE levels vs. subsurface horizons. Conversely, some Bronx River watershed soils showed increased concentrations with depth, reflective of their formation in a thick mantle of construction debris increasing with depth and intermingled with anthrotransported soil materials. Short-range variability was evident in primary pedons and satellite samples (e.g., Pb 253?±?143 mg/kg). Long-range variability was indicated by Pb_TE (348 versus 156 mg/kg) and Hg_TE (1 versus 0.3 mg/kg) concentrations varying several-fold in the same soil but in different geographic locations. Relative predominance of fractions: RES (37 %)?>?SS/CAR (22 %)?>?OX (20 %)?>?OM/S (10 %)?>?EX (7 %)?>?WS (4 %). WS and EX fractions were greatest for Hg (7 %) and Cd (14 %), respectively. RES was predominant fraction for Co, Cr, Ni, and Zn (41 to 51 %); SS/CAR for Cd and Pb (40 and 63 %); OM/S for Cu and Hg (36 and 37 %); and OX for As (59 %).     

全自动石墨消解-原子荧光法测定土壤总汞

采用全自动石墨消解-原子荧光光度法对土壤总汞进行测定,确定最佳消解时间为1 h,消解液最佳用量为8.0 m L。方法在总汞质量浓度为0.2~2.0μg/L范围内具有良好的线性,相关系数为0.999 9,当取样量为0.500 0 g时,检出限为0.002 mg/kg;测定不同标准土壤样品总汞的结果均在保证值范围内,精密度为4.0%~7.0%,加标回收率为95.0%~108.5%;对甘肃省实际土壤及沉积物样品测定进一步验证了方法的适用性。该法适合大批量样品分析,对于提高工作效率有重要意义。