发泡水泥对日光温室黏土砖墙保温蓄热性能的改善效果

为改善老旧黏土砖墙的保温蓄热性能,使用发泡水泥对黏土砖墙进行加厚并进行了试验测试。对照温室黏土砖墙由120 mm黏土砖+100 mm聚苯板+240 mm黏土砖（从室内至室外）构成,试验温室结构、管理与对照温室相同,仅北墙采用200 mm 的发泡水泥对原有黏土砖墙进行了加厚（简称为“改造砖墙”）。通过对比分析2温室墙体在典型晴天和阴天内的温度变化,表明：在晴天夜间,黏土砖墙和改造砖墙外表面温度比室外气温分别高(2.8±0.9)和(0.8±0.2)℃,黏土砖墙和改造砖墙内表面温度比室内气温分别高(1.5±0.5)和(2.4±0.2)℃。在阴天,黏土砖墙全天内表面温度全天低于室内气温,而改造砖墙内表面温度在17：30－次日08：00期间较室内气温高(0.3±0.2)℃。因此,采用发泡水泥加厚黏土砖墙不仅可减少墙体热损失,还能增加墙体夜间散热量。     

墙体材料对日光温室温度环境影响的CFD模拟

日光温室墙体材料影响温室的蓄热保温性能。该研究以室外气象因子为模拟输入条件,分别对复合墙、全砖墙及全苯板墙的12 m跨度日光温室的温度环境进行了模拟,复合墙、全砖墙内的温度分布变化与以往的测试结果一致。以2004年2月18日实测的气候条件为输入条件,模拟得到复合墙温室温度超过全砖墙温室温度最大值为0.8℃,复合墙温室夜间室温超过全苯板墙温室温度最大值为1℃。早晨揭帘前,复合墙中隔热层以内的砖墙及部分隔热层成为放热体,砖墙中靠近室内近1/3的墙体温度高于室内空气温度,而全苯板墙只有内表面附近略高于室内空气温度。白天复合墙、全砖墙及全苯板墙温度均低于室内空气温度,均为吸热体。采用日光温室温度环境动态模拟模型,可以预测不同温室墙体可能形成的室内温度状况,并且根据不同墙体内温度分布,可优选温室墙体结构。     

日光温室墙体蓄放热层温度变化规律研究

墙体的蓄热保温性能决定了日光温室在室外环境作用下的温度变化。该文建立了单一材料墙体的温度变化估算模型,对黏土砖墙、砾石墙、加草黏土墙及夯土墙的温度变化进行了预测;采用CFD方法分析了墙体总厚度相同(0.60 m)和总厚度不同(0.60和0.72m)情况下,复合墙体各方案中蓄热材料层的温度变化特点。单一材料墙体温度变化预测结果显示,导温系数较大的砾石墙内部温度变化较其他墙体传播快;温度波动厚度还与墙内表面温度振幅有关,黏土砖墙内表面振幅从5℃增加到15℃,墙体内部振幅达到0.1℃时的波动厚度从0.42 m增加到0.54 m。此外,由预测的墙体温度变化可以确定单一材料墙体蓄放热层厚度。模型估算的夯土墙温度变化及蓄放热层厚度与已有文献测试值比较,吻合较好。复合墙体温度CFD模拟分析表明,墙总厚度0.60 m不变,蓄热材料层越厚内部温度衰减越快;蓄热材料层厚保持0.36 m,墙总厚度从0.60 m增加到0.72 m时,蓄热材料层温度均值最大升高1.7℃。研究还发现,复合墙体较厚的蓄热材料层比同材料单一材料墙体同厚度处温度衰减快,复合墙体蓄放热层厚度的确定取决于隔热层的位置。单一材料墙体及复合墙体蓄热材料层温度模拟模型可以为日光温室墙体的厚度及组成设计提供理论参考。     

相变蓄热墙体对日光温室热环境的改善

该文以北京市郊区某蔬菜种植基地日光温室为研究对象,将所研制的新型相变蓄热墙体材料应用于日光温室北墙内表面,通过提高温室墙体太阳能集热与蓄热能力,达到提高太阳能热利用效率和改善日光温室热环境的目的。采用40mm厚相变蓄热墙体材料板的试验温室与同尺寸的普通砖墙的对照温室比较,2010年12月21日至2011年1月18日的比较试验结果表明:草帘开启时段(白天),前者后墙表面温度平均提高1～2.7℃,耕作层(0～20cm)土壤平均温度提升0.5℃,室内环境平均温度提升0.2～2.1℃;草帘关闭时段(夜间),试验温室后墙表面温度平均提高2.1～4.3℃,耕作层土壤平均温度提升0.5～1.4℃,室内环境平均温度提升1.6～2.1℃。所研制的相变蓄热墙体材料较好地改善了温室作物生长热环境,提高了日光温室的太阳能热利用率。     

复合相变储能保温砂浆在日光温室中的应用效果

为改善日光温室内作物生长的热环境,该文研制了一种适用于日光温室的石膏基石蜡/膨胀珍珠岩复合相变储能保温砂浆,其相变温度为25.6℃,相变潜热为89.8 k J/kg。并将50 mm的复合相变保温砂浆用于砖墙日光温室的后墙作为试验温室,与无相变材料的原砖墙温室(即对照温室)进行对比试验。在试验周期内,试验温室的室内日最低温度比对照温室平均高出1.5℃,最高可达2.4℃;其中,阴天试验温室的室内温度比对照温室平均高1.6℃;晴天试验温室的室内最高温度比对照温室低1.7℃,室内最大温差比对照温室低3.1℃,夜间(17:00-次日8:00)试验温室室温比对照温室平均高2.7℃;多云期间,试验温室的室内最高温比对照温室低1.4℃,最大温差比对照温室低3.5℃,夜间试验温室室温比对照温室平均高2.3℃;在相同栽培管理条件下,生长旺盛期和坐果期,试验温室的黄瓜植株高度比对照温室分别平均高出17.1和24.6 cm,试验温室内黄瓜的单果质量和单株结果数分别为对照温室的1.4倍和1.3倍,单株产量为对照温室的1.8倍。试验结果表明,复合相变储能保温砂浆具有良好的保温和蓄、放热效果,对日光温室内的热环境具有明显的改善效果,使其更适于黄瓜的生长。     

北疆麦壳砂浆砌块填充蓄热材料复合墙体日光温室热性能

针对新疆戈壁沙漠区日光温室在冬季严寒条件下,传统墙体在夜间难以满足作物生长对热环境需求的问题,该文研究新型的保温蓄热墙体材料和结构。将墙体主体结构采用麦壳砂浆砌块,砌块中间空格填充蓄热材料,对麦壳砂浆砌块进行配比试验和性能测试,筛选出抗压强度、导热性能较优的砌块建造温室墙体,把麦壳砂浆砌块+红砖复合墙体日光温室和37 cm砖混墙体日光温室进行热性能对比试验,并种植番茄验证。试验结果表明:在相同外界环境下,室外最低温-20.8℃时,麦壳砂浆砌块复合墙体日光温室内温度为7.5℃,而砖混墙体日光温室内温度为3.2℃,砌块复合墙体日光温室内夜间出现最低室温时间较砖混墙体日光温室延迟42 min;相同条件下砌块复合墙体日光温室栽培的番茄收获期早16 d,单棚产量高18.4%,验证了砌块复合墙体日光温室的保温蓄热性能优于砖混墙体日光温室,且满足果蔬生长对热环境需求。该文提出的适应戈壁沙漠区日光温室麦壳砂浆砌块复合墙体及构造条件,为新型复合墙体在日光温室中的应用研究、设计提供理论参考。     

日光温室土墙体温度变化及蓄热放热特点

为研究日光温室土墙体温度变化规律及蓄放热特性,以泰安市下挖式土墙日光温室为研究对象,在温室北墙布置5个测试层,通过各测试层最冷季节(30 d)温室内气温、墙体温度、室外气温及室外太阳辐照度测试数据,分析了土墙日光温室内部温度及墙体内温度的分布规律。结果表明:各测试层墙体表面及0.1~0.6 m处测点的温度均呈现出随温室气温周期性变化的规律,且随着墙体厚度的增加温度的波动幅值逐渐减小,相位明显后移;0.7 m以后测点的温度幅值趋于稳定,处于稳态向室外的导热过程。基于墙体温度分布规律,对墙体白天的蓄热量、夜间的放热量及墙体夜间放热效率进行了计算,得出墙体夜间放热效率为43%,表明土墙白天蓄积热量的43%用于改善夜间温室内热环境。对墙体蓄热和放热量计算,综合评价墙体的平均放热效率,可以为土墙日光温室结构优化及热负荷计算提供指导,为各地土墙温室轻简化技术研究提供理论基础。     

基于日光温室相变材料的梯形墙体热特性分析

将以石蜡为主的固-液复合相变材料喷涂到日光温室梯形北墙体内表面,对相变涂层温室梯形墙体和普通温室梯形墙体的热流量、北墙内的温度,以及室内外气温进行典型天气和月度变化的测试分析,以探究相变材料应用于日光温室梯形墙体后对室内热环境的影响。结果表明：晴天和阴天,相变涂层温室墙体的日间蓄热量和夜间放热量均显著高于普通温室墙体（P＜0.05）。相变涂层温室墙体与普通温室墙体在同一典型时刻相同部位温度存在一定差异,这种差异随着墙体深度的增加而逐渐减弱,0-300mm墙体内差异最显著（P＜0.05）。相变涂层温室墙体的累积蓄热量日平均值比普通温室墙体高8.1%,累积放热量日平均值比普通温室墙体高14.8%,相变涂层墙体表面和墙体内各层的月平均温度与普通温室墙体温度差异显著（P＜0.05）,相变涂层温室、普通温室和室外的月平均气温分别为9.93、8.63和-8.91℃。说明相变涂层墙体可有效增加墙体蓄放热量,提升温室气温尤其是夜间气温。     

日光温室平板微热管阵列蓄热墙体热性能试验

为提高日光温室复合结构墙体热稳定层的温度并提升温室墙体材料的蓄热性能,该研究提出一种新型日光温室平板微热管阵列蓄热墙体(Micro Heat Pipe Array,MHPA),搭建了小型MHPA墙体温室试验台,采用对比试验的方法,结合温室墙体温度、墙体蓄放热量以及温室环境温度等评价参数,对比分析了典型日MHPA墙体的蓄放热特性及其改善温室热环境效果。结果表明,与普通温室相比,冬季典型晴天,放热时段(17:00至次日9:00)MHPA墙体内表面平均温度提高1.6～2.3℃,由室内向室外沿墙体厚度方向0～370 mm区域内MHPA墙体内部的平均温度提高2.7～4.0℃;MHPA温室的平均温室环境温度提升1.2～1.5℃,地表面平均温度提升0.6～1.0℃;MHPA墙体的日总蓄热量提高了8.93%～14.35%,日总放热量提高了2.24%～8.07%,且在夜间23:00至次日7:00 MHPA墙体的放热速率高于普通墙体的,平均提升11.53%。因此,MHPA墙体引入于日光温室墙体中可提升温室墙体材料的蓄放热性能,改善温室热环境。该结果可为日光温室平板微热管阵列蓄热墙体的应用提供参考。     

相变材料墙体在郑州地区下沉式日光温室中的保温作用

将以CaCl2为主的水合无机盐复合相变材料平铺一层于郑州地区下沉式日光温室后墙夹层内,以普通温室为对照,观测并探讨典型天气条件下相变温室和普通温室室内温度、后墙内表面温度以及室内外温差变化规律。结果表明,晴天相变温室在揭苫后平均升温速率为3.26℃/h,低于普通温室的3.65℃/h,午后最高温低于普通温室但差异不显著,全天后墙内表面平均温度高于普通温室3.9℃,夜间室内温度高于普通温室1.8℃,室内外温差大于普通温室。阴、雨天相变温室与普通温室的室内温度、后墙内表面温度以及室内外温差均表现出一致的变化趋势;雪天温室内温度以及后墙内表面温度全天呈下降趋势,相变温室温度下降速率高于普通温室0.08℃/h,而相变温室室内外温差变化较小,普通温室室内外温差逐渐变大。相变材料能有效吸收储存热量,提高室内温度。试验结果可为水合无机盐复合相变材料的保温降能耗特性提供理论支持,也可为其在日光温室中的推广应用提供依据。     

低氮和干旱胁迫对富士和秦冠生长及氮素利用的影响

【目的】以富士（Fuji）、 秦冠（Qinguan）嫁接在平邑甜茶（Malus hupehensis Rehd.）上的当年生盆栽苗为试验材料,采用砂培方法,研究了缺氮胁迫和干旱对富士和秦冠生长情况、 光合参数、 植株各部位氮磷钾含量及氮素利用效率的影响,分析比较了低氮干旱条件下富士和秦冠生长及氮素利用的差异,以期为果树生产高效肥水利用提供理论指导。【方法】试验共设四个处理: 正常氮正常水（ZZ）、 低氮正常水（DZ）、 正常氮干旱（ZG）、 低氮干旱（DG）。氮素和水分均设置两个水平,分别为正常氮（6 mmol/L NO-3-N）、 低氮（0.3 mmol/LNO-3-N）、 正常供水（保持盆中砂子相对含水量为饱和含水量的80%~85%）、 干旱处理（保持盆中砂子相对含水量为饱和含水量的60%~65%）。【结果】富士和秦冠的生物量（茎和叶）、 株高茎粗等生长指标以及光合速率、 气孔导度、 蒸腾速率均为正常氮正常水（ZZ）＞低氮正常水（DZ）＞正常氮干旱（ZG）＞低氮干旱（DG）,并且相对应处理下秦冠的以上指标均高于富士;正常供水下,缺氮处理使富士、 秦冠的根冠比比正常氮处理均有所增加,富士提高了2.05%,秦冠提高了22.40%。富士和秦冠的氮、 磷、 钾含量均表现出正常氮正常水（ZZ）＞低氮正常水（DZ）＞正常氮干旱（ZG）＞低氮干旱（DG）; 氮、 钾元素含量在植株各部位的分布顺序依次是叶＞根＞茎,磷元素则是根＞叶＞茎;光合氮素利用效率（PNUE）和氮素利用效率表现为秦冠处理之间差异极显著,富士处理之间差异不显著;秦冠的PNUE和NUE明显高于富士,在低氮正常水（DZ）处理下,秦冠氮肥利用率比富士高42.07%,在低氮干旱（DG）处理下高64.14%;低氮胁迫下富士和秦冠的NUE显著提高,并且秦冠提高的幅度高于富士。【结论】施用氮肥能够显著提高富士与秦冠的干物质量,同等水肥条件下,秦冠生长优于富士;水分亏缺会减少叶片对氮的吸收,干旱条件下适度增施氮肥,可提高果树的抗旱能力;低氮干旱胁迫下秦冠的生长指标、 光合指标及氮素利用效率指标均优于富士,表现出较强的抗低氮干旱胁迫的能力。     

Biodiversity and ecogeography of wild Lactuca spp. in some European countries

Staff members of the Department of Botany of Palacký University in Olomouc and Gene Bank Department – Workplace Olomouc, Research Institute of Crop Production in Prague, Czech Republic, conducted an expedition in seven European countries (Austria, Czech Republic, France, Germany, Italy, the Netherlands, Switzerland) in August/September 1999 to collect wild Lactuca spp. germplasm and study its geographic distribution, ecology and biodiversity. During the mission, more than 600 locations were visited resulting in the collection of 602 seed samples (accessions) of wild Lactuca species and 13 seed samples of related genera (Chondrilla and Mycelis). Lactuca serriola f. serriola, L. serriola f. integrifolia, L. saligna and L. viminea subsp. chondrilliflora were prevalent in southern Europe (Italy, France), however, only L. serriola was common in central and western Europe (Austria, Czech Republic, Germany, Netherlands, Switzerland). The greatest diversity of Lactuca species was found in France, where also the most seed samples (165) were collected. The most characteristic habitats with a high density of Lactuca spp. populations were observed along roads and highways, grassy ditches, ruderal communities, and dust-heaps. Natural infections by powdery mildew (Erysiphe cichoracearum) and downy mildew (Bremia lactucae) on some wild Lactuca spp. were observed. Recent observations concerning the geographic distribution, population structure, habitats, and natural occurrence of diseases of Lactuca spp. are discussed. This assemblage of genetic resources of Lactuca spp. can serve as the basis of future studies of species diversification, spatial population structure, plant microevolution, domestication processes, and genetic variability of host-parasite interactions.     

Pasture Vegetation Elemental Analysis by Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is a new technique for the analysis of plant material. This study investigates the application of LIBS to pasture-based plant samples. The LIBS measurements were obtained from pelletized pasture samples (100 samples) that had been also analyzed by inductively coupled plasma–optical emission spectroscopy (ICP-OES) following microwave digestion for calibration and comparison purposes. Comparisons for elements sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), boron (B), phosphorus (P), and sulfur (S) showed that LIBS could be used for almost all the standard profile total elements with concentrations down to low mg/kg levels (observed error of Na: 0.024 percent, K: 0.18 percent, Mg: 0.016 percent, Ca: 0.073 percent, P: 0.017 percent, Mn: 31 mg/kg, Fe: 150 mg/kg, Zn: 6.6 mg/kg, and B: 1.1 mg/kg). Elemental analysis at less than mg/kg levels was not possible using LIBS. The elements S and Cu were particularly difficult to analyze with reliability using LIBS at the concentration levels found in the plant samples. Replacing microwave digestion and subsequent ICP analysis with a direct analysis of dried plant samples using LIBS has the potential to improve the productivity and reduce the cost of testing.     

Properties of anaerobically digested and composted municipal solid waste assessed by linking soil mesofauna dynamics and nitrogen modelling

We have studied the effect of anaerobically digested (ADMSW) and composted municipal solid waste (CMSW) on mineralization and foodweb dynamics to verify the hypothesis that ADMSW would immobilize N right after addition to soil in contrast to addition with CMSW. Another hypothesis was that the mesofauna (enchytraeids and microarthropods) would stimulate N release from the decomposer community. We measured excretion of -N and urea-N from the mesofauna and hypothesized that enchytraeids would release urea. ADMSW and CMSW were amended to pots with sandy loam and barley. The pots were divided into treatments with or without mesofauna. Mesofauna, plant N and biomass, soil N and ergosterol (fungal biomass) were measured over a 113-day period of four equidistant samplings. Soil respiration, N mineralization and N release by the mesofauna were modelled from concurrent studies. ADMSW- and CMSW-treated soils initially (<20 days) immobilized N. The amendments did not increase plant growth substantially, and this was probably due to N-limitation in the early stages of plant growth. Enchytraeid abundance was about three times higher in ADMSW- than CMSW-treated soils, indicating that ADMSW contained more labile compounds, bacteria, and microfauna. The mesofauna did not affect N-content, but the cumulated -N excreted by the mesofauna was estimated to be substantial and about one-fifth of total plant N in ADMSW. An explanation for this discrepancy might be that in the absence of the mesofauna, other members of the detrivore and microbivore community performed the mesofauna’s function. Neither enchytraeids nor microarthropods excreted urea.     

Faculty positions: Center for Agricultural Resources Research,Chinese Academy of Sciences

正The Center for Agricultural Resources Research(CARR),the Institute of Genetics and Developmental Biology(IGDB),Chinese Academy of Sciences,invites applicants for several research group leader positions.CARR is one of the research organizations in Chinese Academy of Sciences(CAS).We seek nominations and applications from individuals who have expertise and a record of accomplishment in research areas related to ecology,agro-hydrology,     

Faculty positions: Center for Agricultural Resources Research,Chinese Academy of Sciences

正The Center for Agricultural Resources Research(CARR),the Institute of Genetics and Developmental Biology(IGDB),Chinese Academy of Sciences,invites applicants for several research group leader positions.CARR is one of the research organizations in Chinese Academy of Sciences(CAS).We seek nominations and applications from individuals who have expertise and a record of accomplishment in research areas related to ecology,agro-hydrology,     

Faculty positions:Center for Agricultural Resources Research,Chinese Academy of Sciences

正The Center for Agricultural Resources Research(CARR),the Institute of Genetics and Developmental Biology(IGDB),Chinese Academy of Sciences,invites applicants for several research group leader positions.CARR is one of the research organizations in Chinese Academy of Sciences(CAS).We seek nominations and applications from individuals who have expertise and a record of accomplishment in research areas related to ecology,agro-hydrology,     

Macroinvertebrates in North American tallgrass prairie soils: effects of fire, mowing, and fertilization on density and biomass

The responses of tallgrass prairie plant communities and ecosystem processes to fire and grazing are well characterized. However, responses of invertebrate consumer groups, and particularly soil-dwelling organisms, to these disturbances are not well known. At Konza Prairie Biological Station, we sampled soil macroinvertebrates in 1994 and 1999 as part of a long-term experiment designed to examine the effects and interactions of annual fire, mowing, and fertilization (N and P) on prairie soil communities and processes. For nearly all taxa, in both years, responses were characterized by significant treatment interactions, but some general patterns were evident. Introduced European earthworms (Aporrectodea spp. and Octolasion spp.) were most abundant in plots where fire was excluded, and the proportion of the total earthworm community consisting of introduced earthworms was greater in unburned, unmowed, and fertilized plots. Nymphs of two Cicada genera were collected (Cicadetta spp. and Tibicen spp.). Cicadetta nymphs were more abundant in burned plots, but mowing reduced their abundance. Tibicen nymphs were collected almost exclusively from unburned plots. Treatment effects on herbivorous beetle larvae (Scarabaeidae, Elateridae, and Curculionidae) were variable, but nutrient additions (N or P) usually resulted in greater densities, whereas mowing usually resulted in lower densities. Our results suggest that departures from historical disturbance regimes (i.e. frequent fire and grazing) may render soils more susceptible to increased numbers of European earthworms, and that interactions between fire, aboveground biomass removal, and vegetation responses affect the structure and composition of invertebrate communities in tallgrass prairie soils.     

Assessing the effectiveness of conservation measures: Resolving the “wicked” problem of the Steller sea lion

“Wicked” problems are those that are complex and that change when solutions are applied. Many conflicts in conservation fall into this category. The study approached the problem of how to constrain the apparent wickedness of a problem in the conservation management of a species by using simple empirical indicators to carry out iterative assessment of the risk to a population and to document how this risk evolves in relation to the addition of new data and the implementation of management actions. Effects of high levels of uncertainty within data and also concerning population structure were examined through stochastic simulation and by exploration of scenarios. Historical trends in the example used, the Steller sea lion, showed rapid declines in abundance in some regions during the 1980s. The current total population is 130,000-150,000 Steller sea lions through Alaska and British Columbia and this number has been stable since about 1990 in spite of regional differences in population dynamics. Regional differences in the sequence of changes in the number of pups and non-pups, suggested that an internal re-distribution of juveniles could have happened between 1980 and 1990. Current productivity also appears close to the long-term mean. Stochastic population projection using various scenarios showed that, based upon this history, the risk of extinction for the population has declined and is below reasonable thresholds for considering the population to be endangered. The trends in risk suggest that management actions taken since 1990 have probably been effective. Consequently, the conservation management objectives for the Steller sea lion are probably being met. The approach provides a mechanism, based upon experience and scenario analysis, for exploring future policy options and may help to constrain the debate amongst stakeholders about the cost-benefit trade-offs associated with different options.     

Soil-profile distribution of primary and secondary plant-available nutrients under conventional and no tillage

Nutrient distributions under no tillage (NT) compared with conventional disk-and-bed tillage (CT) management in the warm, humid region of the southeastern USA need to be assessed so that future placement, quantity, and type of fertilizers can be altered, if necessary, to efficiently match crop demands. We determined soil-profile distributions of pH, N, P, S, K, Ca, Mg, Na, Zn, Fe, Mn, and Cu to a depth of 0.9 m at the end of 8.5 years of continuous CT and NT management on a Weswood silty clay loam (fine, mixed, thermic Fluventic Ustochrept) in southcentral Texas. Most dramatic changes occurred within the 0–0.05 m depth, where soil under NT had lower pH, Fe, and Cu than under CT, but greater P, K, Zn, and Mn. Greater P and K under NT than under CT also occurred below the till-zone (0.15–0.3 m). At a depth of 0–0.3 m, soil under NT contained greater amounts of extractable P, K, Zn, Fe, Mn, and Cu than under CT. Nitrogen fertilization had little effect on nutrient distributions, except resulting in greater extractable K at 0–0.05 m and greater nitrate at 0–0.15 m. Few changes in soil-profile distributions were observed for extractable S, Ca, Mg, and Na. Long-term continuous use of NT on this fine-textured, high-fertility (except for N) soil had no apparent adverse effects on nutrient distributions relative to CT, but enhanced conservation and availability of P, K, Zn, Fe, Mn, and Cu near the soil surface where crop roots proliferate.