花生秸秆生物炭输入对棕壤中铜形态转化及其有效性的影响

人工模拟铜污染棕壤,通过添加不同裂解温度(350℃、500℃和650℃)和不同施用量(2%和4%)的花生秸秆生物炭,探究生物炭输入对土壤pH和铜形态(Tessier连续提取法)的影响,分析生物炭输入对棕壤铜生物有效性的影响机制。结果表明:随着制备温度的升高,生物炭产率、平均孔径减小,pH、灰分、阳离子交换量(CEC)和比表面积增大;施加生物炭提高了土壤pH,土壤pH与交换态铜含量成负相关,且随生物炭裂解温度和添加量的增加而升高;施炭量一定条件下,随着输入生物炭裂解温度的升高,土壤交换态铜、铁锰氧化物结合态铜含量显著减少(P0.05),有机化合态铜含量显著增加(P0.05),残渣态含量增多,其中650℃裂解温度生物炭处理对降低土壤铜有效性效果最好;在相同的裂解温度下,随着施炭量增加,土壤交换态、碳酸盐结合态和铁锰氧化物结合态铜含量减少,有机化合态铜和残渣态铜含量增多,其中以4%施炭量处理对降低土壤有效态铜的效果最优。研究结果表明,生物炭裂解温度和添加量是影响棕壤pH和铜生物有效性的因子,其中SP4-650处理最有利于降低棕壤中铜生物有效性。     

土壤锌铁铜锰形态分布及其有效性

各土壤微量元素的形态分布特性有相似的规律，每个微量元素的各种形态都可以根据其对植物的有效性划分为两组，第一组形态分布百分率与植物有效性指数呈显著或极显著相关，第二组则显著或极显著负相关，因而第一组的形态为主要的有效养分源，第二组的形态很难为植物提供有效养分，减少相应元素转化为第二组的形态和增加第一组各形态的储备容量是调节和控制土壤营养的重要措施。     

红壤中丛枝菌根真菌对污泥态铜生物有效性的影响

以玉米为宿主植物 ,研究了不同污泥量 (0、1 %、4% )施入红壤后接种丛枝菌根真菌Acaulosporalaevis、Glomuscaledonium和Glomusmanihotis对菌根侵染率、孢子密度、玉米生长和铜生物有效性的影响。结果表明 ,施用 1 %的污泥可增加接种A laevis的菌根侵染率和孢子密度 ,其玉米地上部和地下部生物量也有显著增加 ,而不接种 (含土著菌根真菌 )、接种G caledonium和G manihotis的菌根侵染率、孢子密度、玉米地上部和地下部生物量却有显著下降 (p<0 0 5 )。施用 1 %的污泥时接种A laevis降低了玉米地上部铜浓度 ,而接种G caledonium和G manihotis却增加了玉米地上部铜浓度 ,另外 ,接种处理增加玉米根部对铜的吸收总量。不同的菌根真菌对重金属的耐受力是不同的 ,只有施入一定的污泥量即在一定污染程度下才能发挥菌根真菌A laevis对污染土壤的修复作用     

尾矿库尾砂及周边农田土壤重金属形态分布及其生物有效性

采用BCR（community bureau of reference）连续提取法对大宝山矿山槽对坑尾矿库尾砂和周边农田土壤重金属Cd、Pb、Cu和Zn的形态分布及其生物有效性进行了分析。结果表明,尾砂中Cd、Pb、Cu和Zn残渣态占绝对优势,占其总量的百分数均在85%以上。农田土壤中Cd、Cu和Zn都以残渣态为主,分别占其总量的60%、60%和90%以上,Pb以残渣态和可还原态为主,占其总量的93.44%。农田土壤重金属有效性较尾砂大,尾砂和农田土壤重金属生物有效性均以Pb为最高。     

有机肥对土壤铜形态及其生物效应的影响

通过施用有机肥及增加外源铜的投入,研究了有机肥对土壤中铜的形态及其生物效应的影响。结果表明,增加外源铜的投入和施用有机肥都会改变铜在不同形态间的分配,随外源铜投入量的增加,交换态组分增加的幅度较小,其他形态则增加幅度较大,其中有机结合态、锰结合态的相对比例增加迅速。在200 mg/kg铜处理中,含量分别为无铜对照的28.3倍和25.8倍,占总量的比例分别由17.3%和15.9%上升为39.6%和33.3%。随着有机肥用量的增加,锰结合态组分含量相对降低,在无外源铜投入时其含量在0%和6%有机肥用量下分别为1.77,1.61 mg/kg;当外源铜投入量为200 mg/kg时,0%和6%有机肥处理的锰结合态组分分别为61.48,26.04 mg/kg。有机结合态组分则随有机肥的用量增加而增加,在无外源铜投入时,其含量在0%和6%有机肥水平下分别为1.37,2.45 mg/kg;在外源铜加入量为200 mg/kg时,0%和6%有机肥水平下有机结合态铜分别为25.83,71.83 mg/kg。草莓根系铜含量与各形态铜皆有极显著正相关关系,而地上部铜含量仅与有机结合态铜无显著相关关系,有机肥处理对草莓铜含量也无显著影响。     

施用污泥的土壤重金属元素有效性的影响因素

污泥农用是解决城市污泥出路较为合理的途径,但由于含较高量的重金属,它的应用受到限制,研究发现,进入土壤的重金属在不同的土壤类型不同的土上,形态分布各不相同,而不同形态的重金属对植物的有效性和毒性也不相同,本文试图对土壤中影响重金属形态分布的因素及机制作一综述。     

不同茶园土壤中外源铅的形态转化及其生物有效性

为了明确外源铅进入不同茶园土壤后其形态的转化及其生物有效性,采用盆栽试验及连续浸提形态分级方法,研究了外源铅在不同茶园土壤中的形态分布规律及其在茶树体内的累积分布规律。结果表明,不同母质茶园土壤中铅总量及各形态的含量有明显差异,无外源铅污染的情况下,临安凝灰岩与金华红壤母质茶园土壤以残渣态占主导地位,嵊州玄武岩和梅家坞鞍山母质茶园土壤则以铁锰态铅占主导地位,4种土壤的交换态含量均较低,均在总量的10%以内。当受外源铅污染后,4种茶园土壤中各形态铅均有不同程度的增加,转变为以铁锰态为主,碳酸盐态及可交换态含量在总量中所占比例明显增加,但不同母质土壤类型差异较大。在小于500mg·kg-1土的外源铅污染下,交换态以嵊州玄武岩、临安凝灰岩增幅最大,金华红壤最小;但外源铅达到2500mg·kg-1土时,金华红壤中的交换态铅急剧增加。低浓度外源铅对金华红壤、梅家坞鞍山斑岩茶园土中的茶树生长发育有促进作用,但对嵊州玄武岩和临安凝灰岩茶园土壤中的茶树生长刺激作用并不明显。高浓度的外源铅则对4种土壤中的茶树生长均产生明显的抑制作用,且碳酸盐态与交换态对茶树生长的抑制作用最大。对新梢中的铅而言,金华红壤茶园土壤以有机态铅对其贡献最大,其余3种母质茶园土壤均以碳酸盐态贡献最大;对老叶与茎杆中的铅而言,嵊州玄武岩母质茶园土壤以有机态贡献最大,其余3种土壤均以铁锰态贡献最大;对须根中的铅而言,梅家坞鞍山斑岩茶园土以有机态贡献最大,其他3种土壤均以铁锰态贡献最大。     

上海不同地区土壤中硒的形态分布及其有效性研究

本文研究了上海不同地区土壤中硒的形态分布及其有效性,结果表明,土壤中硒的存在形态与土壤ｐＨ和有机质含量密切相关,土壤中硒主要以有机物－硫化物结合态及元素态存在,占总硒含量在４３～６０％,其次是残渣态,占２３～４３％,而其余三种形态仅占１２～２１％,统计分析表明,可溶态,可交换态及碳酸盐结合态硒对作物最有效,土壤有效硒的ＮａＨＣＯ３和ＫＨ２ＰＯ４浸提法都可以用作判断土壤对作物供硒能力的指标。     

土壤有机磷形态的生物有效性研究

通过对土壤有机磷形态测定及其与土壤有效磷、小麦幼苗吸磷量、黑麦幼苗吸磷量、幼苗试验土壤有机磷矿化量的相关分析,研究了土壤有机磷形态的生物有效性。结果表明:反映土壤供磷状况及植物磷素营养状况的一些相关指标,如有效磷、黑麦草幼苗吸磷量与有机磷组分无明显直线相关关系,不能说明土壤有机磷形态的有效性。而幼苗试验土壤有机磷的矿化量、小麦幼苗吸磷量可以从一个侧面反映土壤有机磷形态的有效性。总的趋势是活性有机磷和中等活性有机磷表现出较高的有效性,高稳性有机磷有效性最低。     

溶解性有机物对土壤中铜生物有效性的影响

采用盆栽试验,研究了模拟铜污染土壤中溶解性有机物（DOM）对红壤、褐土和黑土3种不同类型土壤中小油菜（Brassia campestris）的生长及对Cu生物有效性的影响。结果表明,随着DOM的加入,黑土和红壤中小油菜的出苗率均有所下降,尤其是当DOM添加量大于100mgC·kg^-1时,红壤中小油菜出苗率显著降低（P〈0.05）,而对褐土的出苗率影响不大;供试3种土壤中小油菜生物量均呈先上升后下降的趋势,其在DOM添加量为50mgC·kg^-1时生物量达到最大,但比较而言,3种土壤中小油菜生物量由大至小的顺序为：黑土〉褐土〉红壤;随着土壤中添加DOM浓度的升高,小油菜植株体内铜浓度大致呈现不断增加的趋势,且3种土壤中植株体内的铜浓度均在DOM添加量为200mgC·kg^-1时达最高值,与对照处理及添加量为50mgC·kg^-1处理间差异显著（P〈0.05）;土壤中有效态Cu含量则随DOM量的增加呈不断升高趋势,3种供试土壤有效态Cu含量以红壤最高,当DOM添加量为0-100mgC·kg^-1时,褐土中有效态铜含量高于黑土;而当DOM添加量为150-200mgC·kg^-1时,黑土中的有效态铜含量却高于褐土。这表明随着外源性DOM进入土壤,可导致土壤中Cu的生物有效性不断发生变化,从而直接影响作物的生长以及作物对Cu的吸收。     

Chemical transformation of copper in some sludge-amended soils

In a laboratory incubation study, the periodic changes in different chemical fractions of copper (Cu) in three sludge-amended soil types (acidic sandy clay loam, neutral clay loam and alkaline clay loam) of varying soil reaction were monitored under field capacity and flooding moisture regime over 16 months. The water soluble and exchangeable fraction of Cu was very low (≤1% of total Cu) in all three soil types. At the end of incubation (16 months), the sodium acetate extractable (carbonate sorbed)- and residual-Cu fractions transformed into Fe-Mn oxide fraction, irrespective of moisture regime in all three soil types. However, the extent of transformation varied among soils.     

Chicken-manure-derived biochar reduced bioavailability of copper in a contaminated soil

Purpose

Copper (Cu) contamination has been increasing in land ecosystems due to economic development activities. Excessive amount of Cu in soils is toxic to both plants and microorganisms. Biochar (BC) is known to immobilize soil Cu. The objectives of this research were to investigate the effects of chicken-manure-derived BC (CMB) on Cu immobilization, and growth of native metallophyte Oenothera picensis in a Cu-contaminated soil.

Materials and methods

A Cu-contaminated sandy soil (338 mg Cu kg^?1) was spiked and equilibrated with additional Cu (0, 100, and 500 mg Cu kg^?1). The spiked soil was then amended with CMB (0, 5, and 10 % w/w) and incubated for 2 weeks. The metallophyte was grown on these treatments under greenhouse conditions for 3 months. Pore water solutions were collected from the plant pots every 30 days. After the harvest, soil and pore water pH, soil Cu fractions, pore water Cu concentration, soil microbial activity, plant biomass weight, and Cu concentration in plant parts were determined.

Results and discussion

The CMB increased the pH of soils and soil pore water, and probably also soil major nutrients. It reduced the exchangeable fraction of Cu but increased its organic matter and residual fractions. At the same time, it decreased the Cu concentration in the soil pore water. The CMB increased basal respiration and dehydrogenase activity. The CMB application produced up to three and seven times more root and shoot biomass, respectively. In addition, shoots accumulated lesser Cu than control but roots did more. Plants survived in soil that was spiked with 500 mg Cu kg^?1, only when CMB dose was 10 %.

Conclusions

The CMB affected the Cu uptake in plant by altering the mobility, bioavailability, and spatial distribution of Cu in soils. The increase in available nutrients and decrease in Cu toxicity facilitated plant growth. The increased microbial activity probably also promoted the plant growth and reduced the Cu bioavailability. Therefore, CMB can be used to remediate Cu-contaminated soils.

     

不同氮肥处理对污染红壤中铜有效性的影响

通过室内培养试验,发现不同氮肥处理对污染红壤中铜有效性有显著影响。在培养前期(0~15 d),施用尿素显著降低了红壤水溶态铜和有效态铜含量,而施用硫酸铵和硝酸钙则显著提高了水溶态铜含量,且硝酸钙的作用显著大于硫酸铵,但这两种氮肥对红壤有效态铜含量影响较小;培养60 d后,尿素对该红壤两种形态铜的抑制效应逐渐转为正效应,且硫酸铵的促进作用更为显著;硝酸钙对红壤两种形态铜的促进作用不如尿素。氮肥的施用量对两种形态铜也具有显著影响。同一施氮水平下,水溶态铜含量和有效态铜含量在不同氮肥处理间均达显著差异(硫酸铵>尿素>硝酸钙)。不同氮肥影响红壤铜有效性的主要机制是土壤pH的变化,红壤水溶态铜和有效态铜含量均与pH呈极显著负相关。     

施用污泥后石灰性土壤中铜、锌、镉的植物有效性

The toxicity of trace elements (TEs), such as copper (Cu), zinc (Zn), and cadmium (Cd), often restrict land application of sewage sludge (SS) and there was little information about soil-plant transfer of TEs in SS from field experiments in China. In this study pot and field experiments were carried out for 2 years to investigate the phytoavailability of TEs in calcareous soils amended with SS. The results of the pot experiment showed that the phytoavailability of Zn and Cu in the SS was equal to 53.4%-80.9% and 54.8%-91.1% of corresponding water-soluble metal salts, respectively. The results from the field experiment showed that the contents of total Zn, Cu, and Cd in the soils increased linearly with SS application rates. With increasing SS application rates, the contents of Zn and Cu in the wheat grains initially increased and then reached a plateau, while there was no significant change of Cd content in the maize grains. The bioconcentration factors of the metals in the grains of wheat and maize were found to be in the order of Zn > Cu > Cd, but for the straw the order was Cd > Cu > Zn. It was also found that wheat grains could accumulate more metals compared with maize grains. The results will be helpful in developing the critical loads of sewage sludge applied to calcareous soils.     

Effects of time and temperature on the bioavailability of Cd and Pb from sludge-amended soils

A pot experiment was conducted to compare the behaviour and bioavailability of Cd and Pb from two soils mixed with sewage sludge at three rates (0, 50 and 150 t ha^?1) and maintained at two contrasting ambient temperatures (15°C and 25°C) over a period of one year following the treatments. Ryegrass (Lolium perenne) accumulated Cd and Pb in the sewage sludge treated soils, although accumulation was significantly lower in the soils treated at the high rate (150 t ha^?1) compared to the low rate (50 t ha^?1). Ryegrass grown in the warm environment (25°C) accumulated significantly higher levels of Cd and Pb than that grown in cooler conditions (15°C). Samples of the soils spiked with nitrate salts of Cd and Pb at equivalent rates of metal loading resulted in the ryegrass accumulating much higher levels of both the metals than on the sludge treated soils. Metal uptake by the ryegrass from the sludge treatments increased over successive harvests while that from metal salt treatments decreased. The observed trend of increasing plant metal uptake over time coincided with a trend of decreasing pH in the sludge treatments. However, the concentrations of Cd and Pb extracted by DTPA failed to predict the changes in plant metal uptake. The importance of sewage sludge as both a source and a sink of pollutant metals and the trend of increasing bioavailability over time shown by this experiment are discussed.     

Effect of solid-phase speciation on metal mobility and phytoavailability in sludge-amended soil

Sequential extraction was utilized for partitioning Cd, Cr, Ni, and Zn, in soil and sludge samples into five operationally-defined fractions: exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and residual. The highest amounts of Cd, Ni, and Zn, expressed as per cent of the total, were found in the Fe-Mn oxide fraction of the sewage sludge. Chromium was significantly associated with the organic fraction of the sludge. The residue was the most abundant fraction for all metals studied in the untreated soil, and for Cd and Ni in the sludge-treated soil. The concentration of exchangeable Cd and Cr was relatively low in the untreated soil and did not change much after sludge application, whereas the concentrations of exchangeable Zn increased about 50 times and the concentrations of exchangeable Ni doubled in the sludge-treated soil. The lysimetric experiment revealed an increase in Zn and Ni uptake by ryegrass and in the percentage of metals leached from the soil profile after massive sludge application. In contrast only negligible changes were observed for Cd and Cr. The assumption that mobility and biological availability are related to metal speciation was confirmed by the agreement between the distribution pattern of Cd, Cr, Ni and Zn in the soils, the uptake of the metals by plants and their capacity for leaching out from the soils.     

Speciation of aluminum in soil environments

Although aluminum (Al) is abundant in soil environments, it is not an essential element and it is toxic to most organisms. Since the toxicity of Al depends on their chemical forms, the importance of Al speciation has been recognized worldwide. Difficulties in Al speciation are caused by the complex coordination chemistry of Al for the hydrolysis and formation of polynuclear species with a variable degree of solubility in aqueous solution. Nondestructive analyses, such as nuclear magnetic resonance (NMR) spectroscopy, could supply primarily im-portant information on the chemical forms of Al and may enable to evaluate the results ob-tained by other methodologies. In the present report, NMR spectral characteristics of environmentally important Al-containing components, such as hydoxyaluminum ions, Alinorganic complexes, Al-organic complexes, and primary and secondary minerals, are summarized for the nuclei of ²⁷Al and ²⁹Si determined by solution NMR and solid-state magic angle spinning (MAS) NMR. Applications of NMR techniques to soil science, including speciation of phytotoxic Al in soil environments and whole soil NMR studies, are described.     

Denitrification activity in the root zone of a sludge-amended desert soil

Summary We evaluated potential NO _inf3 ^sup- losses from organic and inorganic N sources applied to improve the growth of cotton (Gossypium hirsutum) on a Pima clay loam soil (Typic Torrifluvent). An initial set of soil cores (April 1989) was collected to a depth of 270 cm from sites in a cotton field previously amended with anaerobically digested sewage sludge or an inorganic N fertilizer. The denitrification potential was estimated in all soil samples by measuring N₂O with gas chromatography. Soils amended with a low or high rate of sludge showed increased denitrification activity over soil samples amended with a low rate or inorganic N fertilizer. All amended samples showed greater denitrification activity than control soils. The denitrification decreased with soil depth in all treatments, and was only evident as deep as 90 cm in the soils treated with the high sludge rate. However, when soils collected from depths greater than 90 cm were amended with a C substrate, significant denitrification activity occurred. These date imply that organisms capable of denitrification were present in all soil samples, even those at depths far beneath the root zone. Hence, denitrification was C-substrate limited. A second series of soil cores taken later in the growing season (July 1989) confirmed these data. Denitrification losses (under laboratory conditions) to a soil depth of 270 cm represented 1–4% of total soil N depending on treatment, when the activity was C-substrate limited. With additional C substrate, the denitrification losses increased to 15–22% of the total soil N.     

Fractionation of chromium in tannery sludge-amended soil and its availability to fenugreek plants

Purpose

Fenugreek (Trigonella foenum-graecum L.) is a medicinal plant with antidiabetic effects. Chromium has been related to better glucose tolerance in humans. The objective of this study was to determine whether tannery sludge could be used for Cr biofortification of fenugreek.

Materials and methods

Soil was mixed with tannery sludge containing 6.03 g Cr kg^?1. All Cr was in the form of Cr(III). Three treatments were disposed: control without sludge, and two treatments with 10 and 20 g sludge kg^?1, respectively. Control and the 10 g sludge kg^?1 treatments received NPK fertilizer to adjust the concentrations of major mineral nutrients to similar levels in all treatments. Soils were potted and planted with fenugreek. Plants harvested at the initial flowering stage were analysed for total Cr, Fe, Zn and Pb. Sequential soil extraction was applied to obtain operationally defined soil Cr fractions.

Results and discussion

Total Cr in all treatments was below or within the allowable range for agricultural soils (100–150 mg kg^?1). In control soils, most Cr was in the residual fraction (HF/HClO₄ digest). Tannery sludge-amended soils incorporated most Cr into the moderately reducible fraction (oxalic acid/ammonium oxalate extract). In fenugreek shoots, Cr concentrations reached 3.2 mg Cr kg^?1, a higher concentration than that reported for other leafy vegetables. Lead concentrations in plant shoots from this treatment were enhanced but hardly exceeded 1 mg Pb kg^?1.

Conclusions

Tannery sludge-amended soils containing Cr within the range of permissible concentrations can increase shoot Cr in fenugreek. Only sludge with low Pb concentrations should be used for Cr biofortification of fenugreek.     

Low biodegradability of fluoxetine HCl,diazepam and their human metabolites in sewage sludge-amended soil

Background, aim, and scope

The European Union banned disposal of sewage sludge (SS) at sea in Europe in 1998. Since that time, the application rate of SS to land has risen significantly and is set to rise further. Fifty-two percent of SS was disposed to land in the UK in 2000. Land application is, thus, possibly an important transport route for SS-associated organic chemicals into the environment. There are now over 3,000 different pharmaceutical ingredients in use in the EU and many enter sewage systems. Possibly as a result, the last decade has seen an increase in reports of pharmacologically active compounds in the environment (e.g. in watercourses, open ocean and soils). Surprisingly, there is still a significant lack of knowledge of the transport and fate of pharmaceuticals in the environment, particularly in soils. The present project, therefore, investigated the susceptibility to microbial degradation of the selective serotonin re-uptake inhibitor, Prozac® (fluoxetine HCl), and the 1,4-benzodiazepine, Valium® (Diazepam) and their major human metabolites (norfluoxetine HCl, temazepam and oxazepam) in short-term (60 day) bacterial liquid cultures derived from UK SS-amended soil and of fluoxetine HCl in a longer-term (270 day) SS-amended soil culture.

Methodology

Recently developed extraction techniques, including solid phase extraction, allowed all analytes to be isolated from the biodegradation cultures (aqueous and soil matrices), and subsequently analysed using novel high performance liquid chromatography–electrospray ionization-multistage mass spectrometry (HPLC-ESI-MSⁿ) techniques. Ratio calibration using deuterated internal standards allowed the generation of quantitative data. A simple basified tautomerism experiment was also performed to aid in the identification of a bacterial transformation product. Alongside the biodegradation studies, HPLC-APCI-MSⁿ profiling of bacteriohopanepolyols (BHPs; bacterial membrane marker chemicals) allowed assessment of the microbial community structure in the SS-amended soils.

Results

The pharmaceuticals were found to be resistant to biodegradation in liquid culture studies (60 days), and even after prolonged exposure in SS-amended soil (>200 days; fluoxetine HCl only). Oxazepam was the only 1,4-benzodiazepine studied which underwent biotic transformation (~40%) in liquid culture studies. Evidence to support the theory that the transformation product was a 1,4-benzodiazepine tautomer, is presented. BHP profiles of eight different SS-amended soils suggested that the restricted bacterial community of the soil used as a culture source in these biodegradation studies was typical of SS-amended soils.

Discussion

The lack of substantial degradation of all target analytes except oxazepam under simulated, but realistic, SS-amended soil conditions indicates their likely persistent nature. Although oxazepam did undergo significant biotic (and abiotic) losses, the metabolite formed under biotic influences was hypothesised to be another bioactive 1,4-benzodiazepine (either 2-enol or 3-enol nordiazepam) which is likely to be resistant to further change. The bacterial communities in SS-amended soils may be unable to degrade such compounds.

Recommendations and perspectives

With such pharmaceuticals as tested here, there is a potential for accumulation within environments such as field soil to which SS is regularly added both as a disposal mechanism and as a fertiliser. When compounds undergo accumulation, the risk of transport to other environmental components becomes more likely. From field soils, these may include potential exposure to flora and fauna and possible bioaccumulation or effects on terrestrial organisms and accumulation in plants, including crops grown on the SS-treated soils. The fate and subsequent impact of many pharmaceuticals within the terrestrial environment is still largely unknown and further research is required before the risks, if any, of SS-associated pharmaceuticals can be fully assessed.