重庆市垃圾焚烧飞灰特性及重金属浸出行为的研究

通过激光粒度仪分析了重庆市垃圾焚烧飞灰颗粒粒径的分布特征,并研究了在GB5085.3-2007和USEPA-TCLP浸出条件下及不同pH、浸出液固比和浸出时间等因素下重庆市垃圾焚烧飞灰中重金属的浸出行为.结果表明,重庆市垃圾焚烧飞灰颗粒平均粒径为36.4μm,飞灰中主要重金属总量约1.04%,Zn、Pb含量较高,具有较...     

硫酸锰废渣浸出毒性及淋溶特性研究

长沙市兴镇13家硫酸锰厂的生产废渣使当地的生态环境造受到了严重破坏。本文在废渣浸出毒性实验、渣柱淋滤实验以及废渣的全分析基础上,全面地研究了废渣的组成、浸出毒性大小以及在当地酸沉降条件下的淋滤特征,为其安全处置提供了理论基础。研究证明,废渣中重金属种类多、含量高,尤其是锰,高达138800mg/kg。渣的浸出毒性虽未达到国家规定的危险废物鉴别标准,但远超过了《污水综合排放标准》,其衰减可用负指数方程来描述。在酸雨淋溶下,渣中的锰离子会在短时期内大量释放后,维持在一相对较低水平长期释放,对环境威胁巨大。     

矿区炼金废渣的固化/稳定化处理

通过对金矿矿区炼金废渣的酸中和能力、净产酸量及浸出毒性实验，测定了废渣的产酸潜力及重金属砷、镉、铅、锌的总量和它们的浸出量。为了合理处置矿区炼金废渣，并为矿区重金属污染土壤的修复提供技术支持，采用石灰、粉煤灰、堆肥化污泥作为添加剂对废渣进行固化/稳定化处理；通过浸出毒性实验对固化/稳定化处理效果进行综合分析，试图寻求一种最佳的稳定剂。结果表明，无论是单独添加石灰、粉煤灰或者堆肥化污泥还是两两组合混合添加，样品浸出液的pH都有升高，As、Cd的浸出浓度都有明显下降，而且两两组合添加比单独添加的固化/稳定化处理效果更好。在两两组合添加中，粉煤灰混合堆肥化污泥的处理效果最好，浸出液的pH值达到7.82，As、Cd的浸出率分别下降72.0%和72.2%。说明粉煤灰混合堆肥化污泥处理炼金废渣效果最佳，同时具有以废治污的资源化生态效能。     

硫酸锰废渣浸出毒性及淋溶特性研究

长沙市黄兴镇13家硫酸锰厂的生产废渣使当地的生态环境造受到了严重破坏。本文在废渣浸出毒性实验、渣柱淋滤实验以及废渣的全分析基础上，全面地研究了废渣的组成、浸出毒性大小以及在当地酸沉降条件下的淋滤特征，为其安全处置提供了理论基础。研究证明，废渣中重金属种类多、含量高，尤其是锰，高达138800mg／kg。渣的浸出毒性虽未达到国家规定的危险废物鉴别标准，但远超过了《污水综合排放标准》，其衰减可用负指数方程来描述。在酸雨淋溶下，渣中的锰离子会在短时期内大量释放后，维持在一相对较低水平长期释放，对环境威胁巨大。     

酸洗-电沉积联用技术回收垃圾焚烧飞灰中的重金属

垃圾焚烧飞灰中的重金属浸出能力强、毒性大,属于危险废物,若处置不当将会对环境造成严重污染。采用酸洗-电沉积联用技术,考察硝酸浓度、液固比和酸洗时间对重金属去除率的影响,研究电沉积电压和时间对酸洗废液中重金属回收率的影响,同时评估处理后飞灰的浸出毒性。结果表明,在浓度为2 mol·L^-1、液固比为25的硝酸中浸渍洗涤60 min条件下,酸洗能成功去除飞灰中95.26%的Zn、83.06%的Pb、72.62%的Cu和97.85%的Cd;在电压为14 V,电沉积4 h的条件下可回收酸洗废液中95.80%的Zn、 99.04%的Pb、79.95%的Cu和90.37%的Cd。对Zn、Pb、Cu、Cd的连续提取和浸出毒性测试表明,处理后飞灰易浸出组分占比降低,残余态物质占比提高,重金属浸出质量浓度符合《生活垃圾填埋场污染控制标准》(GB 16889-2008)要求,可直接进行填埋或作为非危废固体进行资源化利用。本研究结果可为飞灰中重金属脱除和回收利用提供参考。     

粉煤灰合成沸石应用风险评估研究

以粉煤灰为原料通过改良水热法合成了粉煤灰合成沸石,利用扫描电镜(SEM)、X射线衍射(XRD)、BET比表面积等技术手段对其进行了表征;对粉煤灰合成沸石浸出毒性以及出水部分重金属离子浓度进行了实验研究;将使用后的粉煤灰合成沸石与土壤混合用于玉米盆栽实验,同时设置不加粉煤灰合成沸石的对照组,研究使用后粉煤灰合成沸石农用的效果。结果表明:(1)粉煤灰合成沸石主要物相成分为P型沸石,BET比表面积比粉煤灰增加了53倍(从0.867m2/g增加到45.804m2/g)。(2)粉煤灰浸出毒性均低于《危险废物鉴别标准浸出毒性鉴别》(GB 5085.3—2007)规定的浸出毒性鉴别标准值,其中铬、铜、镍未检出;出水部分重金属离子浓度低于《城镇污水处理厂污染物排放标准》(GB 18918—2002)中相应标准值,其中镉、铅、镍均未检出。(3)粉煤灰合成沸石添加于土壤中,对土壤pH影响不大(从6.81升至6.99),但实验组玉米根茎叶长势均好于对照组。     

镍渣的重金属浸出特性

在分析镍渣的矿物相组成和重金属元素含量的基础上,鉴定了镍渣样品的浸出毒性,并考察了pH、液固比和浸出时间等条件对镍渣样中铬、铅、铜和锌等重金属浸出特性的影响。结果表明,镍渣中的重金属总量约为渣样的0.9%,且铬、铜和锌的含量较高,需进行安全管理。实验所用镍渣样品为第Ⅰ类一般工业固体废物。在强酸条件下镍渣中重金属浸出浓度较大,pH3后浸出浓度显著降低;液固比40 L/kg时,镍渣中重金属不断溶出,液固比40 L/kg后,浸出达到饱和,浸出浓度趋于平衡;随着浸出时间的增加,重金属离子的浸出浓度先增加后减少,但由于各重金属性质不同,各重金属达到最大浸出浓度的时间不同。     

基于重金属提取的垃圾焚烧飞灰无害化处理

采用加酸浸出工艺对垃圾焚烧飞灰进行无害化处理。研究证明盐酸能有效分离飞灰中重金属,重金属浸出率与盐酸浓度及液固比有关;重金属在实验的盐酸浓度和液固比下都能达到高浸出率,但液固比越低,浸出液中重金属的浓度就越高,越有利于重金属的回收。当盐酸浓度为5 mol·L~(-1)、液固比为2(mL:g)时,Pb、Cd和Zn浸出率均达到95%以上,而Cu的浸出率也达到81.38%,Pb、Cd、Zn和Cu的浓度分别为468.10、78.12、2 268.80和347.78 mg·L~(-1)。残灰采用加盐水洗工艺后,浸出毒性超标的重金属Pb和Cd浸出毒性低于GB 16889-2008标准限值,符合填埋要求。     

再生铝飞灰重金属的浸出毒性特征及其控制

采用再生铝飞灰为研究样品,研究了飞灰重金属浸出毒性水平以及飞灰浸出毒性特征,同时探讨了飞灰的处理处置工艺。结果表明:飞灰中Pb、Cd和Zn浸出浓度超标,超标率为100%,属于具有浸出毒性的危险废物,必须对其进行稳定和固化;再生铝飞灰中锌的浸出浓度所占比例最大,铅的浸出浓度次之,两者之和占总量的98%以上,再生铝飞灰中主要有害重金属为Zn和Pb;并结合当前飞灰的处理处置工艺,提出的可能的控制方法为水泥固化和药剂稳定法,为同类研究提供参考。     

含锌铅废物碱法浸出工艺

各种工业过程中产生的大量含锌铅废物中含有大量的有毒重金属.必须在危险废物处置场所进行处置,这导致处置成本增加.采用强碱浸出的方法回收含锌铅废物中的Zn和Pb,考察了浸出温度、NaOH浓度、液固比(浸提液体积/原料质量)和搅拌速率等工艺参数对Zn、Pb和杂质金属浸出率的影响,得出其最佳工艺条件.在温度为70℃、液固比为13:1、搅拌速率为800r/min条件下.用5 mol/L的NaOH浸出含锌铅废物,浸出液中Zn和Pb的质量浓度分别达33.47、11.21 g/L,浸出率分别达到94.24%和93.47%.     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

Radionuclides in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

Radionuclides in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.