黄磷废水中氟化物的物化处理研究

本文利用向含氟废水中加入适量石灰和聚合氯化铝PAC ,然后投加适量钙盐、磷酸和聚丙烯酰胺PAM的二级处理工艺除氟。通过控制合适的 pH、钙盐和磷酸的投加量、反应时间、反应温度、搅拌强度和絮凝剂的投加量 ,确定了最佳的除氟工艺 ,可以使氟的浓度降至 5mg/L ,达到国家一级排放标准GB8978 1996。     

铝型材含氟镍酸性废水二级处理工艺

对铝型材含氟镍废水加入Ca(OH)2中和沉淀后,用盐酸回调p H,加Ca Cl2进行二级处理。一级反应过程中加Ca(OH)2将p H值控制在10.0~10.5范围,二级反应过程中加5%盐酸将p H值回调到7~8后,再投加2 g/L的Ca Cl2和10 m L/L的0.1%PAM,处理后水质达到《污水综合排放标准》(GB8978-1996)一级排放要求。该工艺运行稳定,处理效果好,值得推广。     

黄磷废水中氟化物的物化处理研究

本文利用向含氟废水中加入适量石灰和聚合氯化铝PAC，然后投加适量钙盐、磷酸和聚丙烯酰胺PAM的二级处理工艺除氟。通过控制合适的pH、钙盐和磷酸的投加量、反应时间、反应温度、搅拌强度和絮凝剂的投加量，确定了最佳的除氟工艺，可以使氟的浓度降至5mg/L，达到国家一级排放标准GB8978－1996。     

络合沉淀结合混凝法去除浮选废水中有机磷

广西某铅锌矿选矿厂用含磷有机浮选药剂苯胺黑药(学名:二苯胺基二硫代磷酸)和丁铵黑药(学名:二丁基二硫代磷酸铵)作捕收剂,导致尾矿库溢流口外排废水总磷超标(总磷浓度为1.4~1.7 mg/L,p H=8.0)。实验研究表明,含巯基磷酸盐浮选废水中总磷主要为有机磷(占94%),钙盐、铁盐和铝盐混凝沉淀法对有机磷去除效果很差,3种金属离子不能与巯基磷酸盐反应生成沉淀物;但铜离子能与巯基磷酸盐生成溶度积很小的络合沉淀物,再通过混凝沉淀对有机磷可达到很好的去除效果。先加入硫酸铜20 mg/L进行络合沉淀反应,后再加入40 mg/L硫酸铝和1 mg/L PAM混凝沉淀,总磷去除率可达80%。处理后废水总磷浓度和重金属浓度均达到《铅、锌工业污染物排放标准(GB25466-2010)》排放要求。研究结果为该选矿厂浮选废水净化处理和回用工程的设计提供了科学依据。     

诱导结晶法去除地下水中氟离子

针对现行高氟地下水处理工艺中存在的工艺复杂、运行管理困难等问题,提出采用诱导结晶法除氟。其技术核心是在高氟水中投加氟磷灰石作为晶种,并投加磷酸盐和钙盐使水中氟离子在晶种表面生成氟磷酸钙(Ca10(PO4)6F2)结晶。通过单因素实验得出最佳工艺条件:投加8g/L氟磷灰石,并投加NaH2PO4和CaCl2,使钙离子、磷酸根离子和氟离子的摩尔比为10∶5∶1,搅拌速度为100 r/min,反应时间1 h。反应中磷酸根离子和钙离子的利用率分别达到98%和25%以上。电子扫描显微镜(SEM)表征晶种在参与反应后,表面有结晶生成。研究表明,采用诱导结晶法可将水中氟离子浓度从5~10 mg/L降至1 mg/L以下,达到饮用水水质标准。     

采用泥回流处理彩色显像管含氟废水

本文通过中和、混凝沉降法除氟过程,研究了彩色显像管工业废水除氟的适宜工艺条件。现场试验表明:应用泥回流处理技术,采用高效絮凝剂处理含氟废水,排放废水氟含量可稳定在4-6mg/L之间,低于排放标准（10mg/L）,同时废水处理的成本大大降低。     

采用泥回流处理彩色显像管含氟废水

本文通过中和、混凝沉降法除氟过程，研究了彩色显像管工业废水除氟的适宜工艺条件，现场试验表明：应用泥回流处理技术，采用高效絮凝剂处理含氟废水，排放废水氟含量可稳定在4-6mg/L之间，低于排放标准（10mg/L），同时废水处理的成本大大降低。     

焦化废水除氰工艺的优化研究

对某焦化厂生化出水进行了除氰研究。对硫酸亚铁混凝除氰法进行了优化,采用沉淀净化法对其出水进行深度处理,考察了工艺中不同影响因素对总氰化物(TCN)去除效果的影响。结果表明,硫酸亚铁混凝除氰法的最佳反应条件为pH 5.00、FeSO4·7H2O投加量500mg/L、反应时间15min、沉淀时间30min;在此条件下,当原水TCN质量浓度为3.1~4.1mg/L时,出水TCN质量浓度达到0.60~0.70mg/L,需作进一步的深度处理。采用沉淀净化法处理硫酸亚铁混凝除氰法出水的最佳反应条件为先同时投加药剂A和药剂B,投加量分别为150、0.75mg/L,反应15min后,再按2mg/L投加药剂C,继续反应3min,最终出水TCN质量浓度低于0.1mg/L,达到《炼焦化学工业污染物排放标准》(GB 16171—2012)要求(氰化物排放限值为0.2mg/L);在此条件下,单位废水处理的药剂成本合计约为0.25元/t。     

RPB-O3/H2O2法处理硝基苯模拟废水

在超重力场中,研究了硝基苯模拟废水的臭氧/双氧水(O3/H2O2)法处理效果,考察了超重力因子β、H2O2浓度、初始p H、液体流量及处理时间等因素对硝基苯去除率的影响。结果表明,硝基苯去除率随超重力因子β和处理时间的增加而增大,而随H2O2浓度、初始p H和液体流量的增加呈先增大后降低的趋势。当硝基苯初始浓度300 mg/L,工艺条件β=80、p H=10.0、臭氧质量浓度约为40 mg/L、H2O2浓度为4.9 mmol/L、液体流量为120 L/h时,循环处理35 min硝基苯去除率可达96.7%。处理时间60 min后,废水中硝基苯含量1.4 mg/L,COD为39 mg/L,达国家一级排放标准(GB 8978-1996)。在此条件下,硝基苯的降解过程符合准一级反应动力学。     

复合赤泥在高浓度含磷废水处理中的应用

赤泥与石灰粉（CaO和Ca（OH）₂）按不同比例混合制成复合赤泥,通过投加实验考察了复合赤泥的除磷效果。结果证明,对于磷酸盐浓度为45 000 mg/L左右（以P计）的酸性工业废水,复合赤泥（赤泥与Ca（OH）₂按质量比1：1混合）投加量为240 g/L,去除率为99.97%;对于10 mg/L左右的含磷废水,赤泥的最佳投加浓度为15 g/L,上清液磷浓度可降至0.30 mg/L,出水低于0.5 mg/L的排放标准。根据以上研究结果,提出了对高浓度酸性磷酸盐废水的处理宜采用复合赤泥再加原状赤泥的二级处理方法。     

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.     

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.     

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.     

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.     

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.     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

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.     

Biochemical interaction of six op delayed neurotoxicants with several neurotargets

Abstract

Five organophosphorous insecticides: Leptophos, EPN, Cyano‐fenphos, trichloronate and salithion proved to cause irreversible ataxia not only to chicken but also to mice and sheep. TOCP was included as a reference. Cyanofenphos blocked the catecholamine B‐receptor binding activity with ³H‐norepinephrine at a level similar to that of the specific inhibitor propranolol in the mouse heart preparation. In the lamb heart preparation, the B‐receptor was more sensitive to Leptophos, salithion and TOCP than to propranolol. The six compounds and their oxons were screened for their in‐vitro inhibition to monamine oxidase (MAO), acetyl cholinesterase (AChE) and neurotoxic esterase (NTE) in the brain of either mouse, lamb or chicken. It is believed that their AChE inhibition stands for their acute toxicity, while NTE inhibition is responsible for their paralytic ataxia.     

Phytoextraction of lead-contaminated soil using vetivergrass (<Emphasis Type="Italic">Vetiveria zizanioides</Emphasis> L.), cogongrass (<Emphasis Type="Italic">Imperata cylindrica</Emphasis> L.) and carabaograss (<Emphasis Type="Italic">Paspalum conjugatum</Emphasis> L.)

Background, Aims and Scope The global problem concerning contamination of the environment as a consequence of human activities is increasing. Most of the environmental contaminants are chemical by-products and heavy metals such as lead (Pb). Lead released into the environment makes its way into the air, soil and water. Lead contributes to a variety of health effects such as decline in mental, cognitive and physical health of the individual. An alternative way of reducing Pb concentration from the soil is through phytoremediation. Phytoremediation is an alternative method that uses plants to clean up a contaminated area. The objectives of this study were: (1) to determine the survival rate and vegetative characteristics of three grass species such as vetivergrass, cogongrass and carabaograss grown in soils with different Pb levels; and (2) to determine and compare the ability of the three grass species as potential phytoremediators in terms of Pb accumulation by plants. Methods The three test plants: vetivergrass (Vetiveria zizanioides L.); cogongrass (Imperata cylindrica L.); and carabaograss (Paspalum conjugatum L.) were grown in individual plastic bags containing soils with 75 mg kg⁻¹ (37.5 kg ha⁻¹) and 150 mg kg⁻¹ (75 kg ha⁻¹) of Pb, respectively. The Pb contents of the test plants and the soil were analyzed before and after experimental treatments using an atomic absorption spectrophotometer. This study was laid out following a 3 × 2 factorial experiment in a completely randomized design. Results On the vegetative characteristics of the test plants, vetivergrass registered the highest whole plant dry matter weight (33.85–39.39 Mg ha⁻¹). Carabaograss had the lowest herbage mass production of 4.12 Mg ha⁻¹ and 5.72 Mg ha⁻¹ from soils added with 75 and 150 mg Pb kg⁻¹, respectively. Vetivergrass also had the highest percent plant survival which meant it best tolerated the Pb contamination in soils. Vetivergrass registered the highest rate of Pb absorption (10.16 ± 2.81 mg kg⁻¹). This was followed by cogongrass (2.34 ± 0.52 mg kg⁻¹) and carabaograss with a mean Pb level of 0.49 ± 0.56 mg kg⁻¹. Levels of Pb among the three grasses (shoots + roots) did not vary significantly with the amount of Pb added (75 and 150 mg kg⁻¹) to the soil. Discussion Vetivergrass yielded the highest biomass; it also has the greatest amount of Pb absorbed (roots + shoots). This can be attributed to the highly extensive root system of vetivergrass with the presence of an enormous amount of root hairs. Extensive root system denotes more contact to nutrients in soils, therefore more likelihood of nutrient absorption and Pb uptake. The efficiency of plants as phytoremediators could be correlated with the plants’ total biomass. This implies that the higher the biomass, the greater the Pb uptake. Plants characteristically exhibit remarkable capacity to absorb what they need and exclude what they do not need. Some plants utilize exclusion mechanisms, where there is a reduced uptake by the roots or a restricted transport of the metals from root to shoots. Combination of high metal accumulation and high biomass production results in the most metal removal from the soil. Conclusions The present study indicated that vetivergrass possessed many beneficial characteristics to uptake Pb from contaminated soil. It was the most tolerant and could grow in soil contaminated with high Pb concentration. Cogongrass and carabaograss are also potential phytoremediators since they can absorb small amount of Pb in soils, although cogongrass is more tolerant to Pb-contaminated soil compared with carabaograss. The important implication of our findings is that vetivergrass can be used for phytoextraction on sites contaminated with high levels of heavy metals; particularly Pb. Recommendations and Perspectives High levels of Pb in localized areas are still a concern especially in urban areas with high levels of traffic, near Pb smelters, battery plants, or industrial facilities that burn fuel ending up in water and soils. The grasses used in the study, and particularly vetivergrass, can be used to phytoremediate urban soil with various contaminations by planting these grasses in lawns and public parks. ESS-Submission Editor: Dr. Willie Peijnenburg (wjgm.peijnenburg@rivm.nl)