鸟粪石法回收制肥工业废水中氨氮的中试研究

制肥工业废水中氨氮浓度高,难以直接进行生化反应,采用鸟粪石沉淀法可有效去除并回收氨氮。利用中试反应器回收某制肥工业废水中的氨氮,采用氯化镁与氧化镁作为联用镁源,通过考察不同进料方式、搅拌速度、停留时间等因素的影响,确定了鸟粪石法回收氨氮的最佳工况:采用间歇进水、固体投加镁源的投料方式,搅拌速度300 r/min,停留时间2 h。最佳条件下,氨氮去除率达到93.5%,磷残余率小于0.3%,生成的鸟粪石纯度可达85.6%,砷和铅的质量分数分别为0.0036和0.0008,符合肥料中重金属限值(GB/T 23349-2009),其他重金属均未检出。因此,回收产品有很好的利用价值。经济分析表明磷源是此方法处理成本较高的主要原因。     

鸟粪石结晶沉淀法处理氨氮废水的应用研究

论述了鸟粪石的形成机理、形成的影响因素。在废水处理中采用鸟粪石沉淀法脱氮，具有氨氮去除率高、反应速度快、污泥体积小的优点，同时可以回收氨氮。作为缓释肥，具有良好的经济效益。重点介绍了鸟粪石沉淀法处理氨氮废水目前的研究进展，并探讨了该技术在今后的研究趋势。     

酸性条件下剩余污泥中Ca2＋和Mg2＋溶出对磷回收的影响

为了在酸性条件下实现剩余污泥中磷的高效回收，对pH=3时剩余污泥水解酸化过程中氨氮、正磷酸盐和钙镁离子的溶出现象以及磷回收进行了研究分析。结果表明：当pH=3时，所溶出的氨氮、镁离子和钙离子与磷酸盐的摩尔比均大于1，能满足采用鸟粪石沉淀法或者羟磷灰石沉淀法回收磷的要求；但所溶出的钙镁离子的摩尔比大于1，会对鸟粪石沉淀法回收磷的顺利进行有较大影响；有无外加镁剂对磷回收率影响不大。采用改型后的镁型强酸性阳离子交换树脂进行离子交换可以得到较高纯度的鸟粪石沉淀产品，通过XRD检测其纯度为95％以上。     

酸性条件下剩余污泥中Ca2+和Mg22++溶出对磷回收的影响

为了在酸性条件下实现剩余污泥中磷的高效回收，对pH=3时剩余污泥水解酸化过程中氨氮、正磷酸盐和钙镁离子的溶出现象以及磷回收进行了研究分析。结果表明：当pH=3时，所溶出的氨氮、镁离子和钙离子与磷酸盐的摩尔比均大于1，能满足采用鸟粪石沉淀法或者羟磷灰石沉淀法回收磷的要求；但所溶出的钙镁离子的摩尔比大于1，会对鸟粪石沉淀法回收磷的顺利进行有较大影响；有无外加镁剂对磷回收率影响不大。采用改型后的镁型强酸性阳离子交换树脂进行离子交换可以得到较高纯度的鸟粪石沉淀产品，通过XRD检测其纯度为95%以上。     

鸟粪石循环利用处理高氨氮废水的热解行为

为了循环利用鸟粪石处理高氨氮废水,探讨了鸟粪石煅烧与加碱热解的脱氮率,利用电镜扫描(SEM)和X射线衍射(XRD)对2种热解产物进行了分析。鸟粪石煅烧条件为:温度100～225℃,时间1～5 h;加碱热解条件为:温度60～95℃,时间0.5～4 h,加碱量OH-∶NH4+摩尔比值0.4～1.5。结果表明,虽然XRD分析显示2种热解产物都已失去鸟粪石的特征峰,但是鸟粪石加碱热解效果更好,最佳热解条件为:加碱量OH-∶NH4+摩尔比值1,温度90℃,时间2 h,鸟粪石脱氮率95%以上;加碱热解产物表面为多孔状,完全失去了晶体结构;煅烧热解鸟粪石脱氮率仅为80%左右,热解产物晶体结构破坏不完全。鸟粪石在最佳条件下热解循环处理高氨氮废水,可循环使用6次,氨氮去除率80%以上,出水磷浓度小于8 mg/L。     

电化学沉淀法从废水中回收鸟粪石

从废水中以鸟粪石方式去除氮磷通常采用投加化学试剂或吹脱CO2调节p H来实现,少有采用电化学沉淀法回收鸟粪石的应用。为探讨电化学沉淀法回收鸟粪石的可行性,实验采用电解法调节p H,进行了Ⅰ、Ⅱ2个系列的实验,以确定回收鸟粪石的最优操作条件。Ⅰ实验以不锈钢网为阴极,碳棒为阳极,Ⅱ实验采用不锈钢网为阴极,镁棒为阳极。结果表明,(1)鸟粪石沉积物大部分富集在不锈钢网上,便于收集;(2)当碳棒为阳极时,最适电解电压为3 V,镁棒为阳极时,则为3.6 V;(3)不搅拌或低速搅拌有利于鸟粪石的形成,温度对电解反应影响不大;(4)低浓度Ca2+基本不影响电解反应速度,而高浓度Ca2+不仅影响反应速度,还影响鸟粪石纯度;(5)以镁棒或碳棒处理污泥脱水滤液效果接近,都能得到高纯度鸟粪石,且能节省开支。     

以农田高盐排水为替代镁源回收养殖废水中的磷素

为解决新疆南疆地区养殖废水高浓度氮磷和农田排水中的高浓度盐分的协同污染问题,以农田高盐排水为镁源对模拟养殖废水中的磷进行了回收实验,对比了高盐排水和常规镁源的磷回收效率,探讨了影响其回收的主要因素,并通过正交试验获得了高盐排水回收磷的最优反应条件.与常规MgC12镁源的磷回收对比分析结果表明,pH=10时高盐排水回收磷的效率最高,比MgCl2镁源达最大回收率所需的反应pH略高;利用L34正交试验探究了pH(8、9、10、11)、Mg:P摩尔比(1.0、1.5、2.0、2.5)、N:P摩尔比(1.0、1.5、2.0、4.0)对高盐排水镁源回收磷的影响,并结合SPSS统计分析得到高盐排水回收磷的最优反应条件为pH=10、n(Mg):n(P)=2.5,n(N):n(P)=4;高盐排水中的HCO3-和SO42-离子对磷回收有抑制作用,而Ca2+离子对磷回收有促进作用;XRD和SEM-EDS分析表明,高盐排水回收磷的产物以鸟粪石为主,并夹杂着磷灰石和粘土矿物等杂质.整体上,以高盐排水作为替代镁源回收磷的效果较好,本研究为解决鸟粪石沉淀法的镁源问题提供了一种新思路.     

工艺条件对鸟粪石晶体的粒径和沉降速度的影响

采用激光粒度仪实验测定了小型套管式空气曝气填料层磷回收装置中不同条件下生成的鸟粪石晶体的体积平均粒径，考察了其变化规律，并结合Stokes公式计算了晶体的沉降速率，同时考虑鸟粪石晶体形状的影响，进行了相应的修正。实验结果表明，鸟粪石的粒径在10—200μm之间，主要集中于20～100μm；在磷回收装置中添加填料并通人空气有利于增大鸟粪石晶体的粒径和沉降速度，无填料无空气时和有填料有空气时的平均粒径分别在30～55μm和40～65μm之间。随着pH值的增大，鸟粪石晶体的粒径和沉降速度逐渐增大，但当pH大于9．0后，鸟粪石晶体的粒径和沉降速度又逐渐减小；氮磷比值从1：1增大到2：1，鸟粪石晶体的粒径和沉降速度小幅度增加，氮磷比进一步增大，鸟粪石晶体的粒径和沉降速度基本不变；镁磷摩尔比在1：1—1．2：1的范围内时，鸟粪石晶体的平均粒径和沉降速度随镁磷比的增大而增大；镁磷摩尔比大于1．2：1后，鸟粪石晶体的平均粒径和沉降速度随镁磷比的增大逐渐减小；初始磷浓度越高，鸟粪石晶体的平均粒径和沉降速度越大。     

工艺条件对鸟粪石晶体的粒径和沉降速度的影响简

采用激光粒度仪实验测定了小型套管式空气曝气填料层磷回收装置中不同条件下生成的鸟粪石晶体的体积平均粒径，考察了其变化规律，并结合Stokes公式计算了晶体的沉降速率，同时考虑鸟粪石晶体形状的影响，进行了相应的修正。实验结果表明，鸟粪石的粒径在10~200 μm之间，主要集中于20~100 μm；在磷回收装置中添加填料并通入空气有利于增大鸟粪石晶体的粒径和沉降速度，无填料无空气时和有填料有空气时的平均粒径分别在30~55 μm和40~65 μm之间。随着pH值的增大，鸟粪石晶体的粒径和沉降速度逐渐增大，但当pH大于9.0后，鸟粪石晶体的粒径和沉降速度又逐渐减小；氮磷比值从1：1增大到2：1，鸟粪石晶体的粒径和沉降速度小幅度增加，氮磷比进一步增大，鸟粪石晶体的粒径和沉降速度基本不变；镁磷摩尔比在1：1~1.2：1的范围内时，鸟粪石晶体的平均粒径和沉降速度随镁磷比的增大而增大；镁磷摩尔比大于1.2：1后，鸟粪石晶体的平均粒径和沉降速度随镁磷比的增大逐渐减小；初始磷浓度越高，鸟粪石晶体的平均粒径和沉降速度越大。     

铁炭微电解法预处理超高盐榨菜腌制废水

超高盐榨菜腌制废水是高盐、高氮磷及高有机物废水，目前常采用生物方法进行处理，但因高污染物浓度及高盐度影响，处理效果不够理想；因此，选用铁炭微电解法对超高盐榨菜腌制废水进行预处理。通过静态烧杯实验，研究了反应时间、初始pH、铁炭体积比和铁水体积比对COD和氨氮去除率的影响。单因素实验的最佳处理条件：原水pH4～4．5，反应时间为30min，铁炭体积比为1：1，铁水体积比为2：1，出水COD和氨氮的去除率分别为57．29％和53．11％，盐度由原水的6．62％下降为3．63％，去除率达45．17％，pH由原水4．01升高为6．38。正交实验结果表明，影响COD和氨氮去除率的因素从大到小的顺序为：铁水体积比、初始pH、反应时间、铁炭体积比。实验表明，采用铁炭微电解法能够对超高盐榨菜腌制废水中的COD和氨氮进行有效去除，出水的pH升高和盐度下降，能满足后续生物处理的预处理要求。     

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.     

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.     

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.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State—Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, α and β endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino – Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6 % leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (α-endosulfan), 1.47E-162 (β-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

Endosulfan in China 2—emissions and residues

Background, aim, and scope  Endosulfan is one of the organochlorine pesticides (OCPs) and also a candidate to be included in a group of new persistent organic pollutants (UNEP 2007). The first national endosulfan usage inventories in China with 1/4° longitude by 1/6° latitude resolution has been reported in an accompanying paper. In the second part of the paper, we compiled the gridded historical emissions and soil residues of endosulfan in China from the usage inventories. Based on the residue/emission data, gridded concentrations of endosulfan in Chinese soil and air have been calculated. These inventories will provide valuable data for the further study of endosulfan. Methods  Emission and residue of endosulfan were calculated from endosulfan usage by using a simplified gridded pesticide emission and residue model—SGPERM, which is an integrated modeling system combining mathematical model, database management system, and geographic information system. By using the emission and residue inventories, annual air and soil concentrations of endosulfan in each cell were determined. Results and discussion  Historical gridded emission and residue inventories of α- and β-endosulfan in agricultural soil in China with 1/4° longitude by 1/6° latitude resolution have been created. Total emissions were around 10,800 t, with α-endosulfan at 7,400 t and β-endosulfan at 3,400 t from 1994 to 2004. The highest residues were 140 t for α-endosulfan and 390 t for β-endosulfan, and the lowest residues were 0.7 t for α-endosulfan and 170 t for β-endosulfan in 2004 in Chinese agricultural soil where endosulfan was applied. Based on the emission and residue inventories, concentrations of α- and β-endosulfan in Chinese air and agricultural surface soil were also calculated for each grid cell. We have estimated annual averaged air concentrations and the annual minimum and maximum soil concentrations across China. The real concentrations will be different from season to season. Although our model does not consider the transport of the insecticide in the atmosphere, which could be very important in some areas during some special time, the estimated concentrations of endosulfan in Chinese air and soil derived from the endosulfan emission and residue inventories are in general consistent with the published monitoring data. Conclusions  To our knowledge, this work is the first inventory of this kind for endosulfan published on a national scale. Concentrations of the chemical in Chinese air and agricultural surface soil were calculated for each grid cell. Results show that the estimated concentrations of endosulfan in Chinese air and soil agree reasonably well with the monitoring data in general. Recommendations and perspectives  The gridded endosulfan emission/residue inventories and also the air and soil concentration inventories created in this study will be updated upon availability of new information, including usage and monitoring data. The establishment of these inventories for the OCP is important for both scientific communities and policy makers.     

Impact of spiked concentrations of Cd,Pb, As and Zn in growth medium on elemental uptake of Nasturtium officinale (Watercress)

This study is aimed at investigating the impact of water quality on the uptake and distribution of three non-essential and toxic elements, namely, As, Cd and Pb in the watercress plant to assess for metal toxicity. The plant was hydroponically cultivated under greenhouse conditions, with the growth medium being spiked with varying concentrations of As, Cd and Pb. Plants that were harvested weekly for elemental analysis showed physiological and morphological symptoms of toxicity on exposure to high concentrations of Cd and Pb. Plants exposed to high concentrations of As did not survive and the threshold for As uptake in watercress was established at 5 ppm. Translocation factors were low in all cases as the toxic elements accumulated more in the roots of the plant than the edible leaves. The impact of Zn on the uptake of toxic elements was also evaluated and Zn was found to have an antagonistic effect on uptake of both Cd and Pb with no notable effect on uptake of As. The findings indicate that phytotoxicity or death of the watercress plant would prevent it from being a route of human exposure to high concentrations of As, Cd and Pb in the environment.     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

Malathion-induced sublethal toxicity on the hematology of cricket frog (Fejervarya limnocharis)

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on hematological parameters of the cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable hematological alterations were observed. The study on hematological parameters revealed a highly significant decrease (P < 0.01) in the total erythrocytes count in malathion-exposed animals from 24 hours to 96 hrs of exposure as compared to control. Significant decreases (P < 0.01) of hemoglobin and packed cell volume were also observed from 48 hrs to 240 hrs. A significant increase (P < 0.01) in leucocytes count was noted throughout the exposure period. Elevated numbers of lymphocytes and eosinophils as found in the present study revealed lymphocytosis as well as eosinophilia, suggesting that this was a result of direct stimulation of the immunological defense due to the presence of a toxic substance or may be associated with tissue damage. The cytomorphological and cytopathological study of erythrocytes and leucocytes in malathion-exposed frogs at 0.006 ppm concentration revealed various cytotoxic effects at different exposure times. It was noted that the size and the shape of the erythrocytes were subjected to variation in different blood disorders.     

Relation between forest vegetation, atmospheric deposition and site conditions at regional and European scales

Several monitoring programs have been set up to assess effects of atmospheric deposition on forest ecosystems. The aim of the present study was to evaluate effects on the understorey vegetation, based on the first round of a regional (the Netherlands) and a European forest monitoring program. A multivariate statistical analysis showed surprisingly similar results for both data sets; the vegetation appeared to be largely determined by the ‘traditional’ factors soil, climate, and tree species, but there was a small but statistically significant effect of atmospheric deposition. The effects of deposition include a slight shift towards nitrophytic species at high N deposition in the European network, and towards acidophytic species at high S-deposition in the Dutch network. The relatively small effect of atmospheric deposition is understandable in view of the very large natural variation in environmental conditions. Time series of both vegetation and environment are needed to assess deposition effects in detail.