牛粪好氧发酵挥发性物质排放特征及恶臭物质分析

不同原料好氧发酵产生的臭气物质组分和浓度存在差异。以牛粪和玉米秸秆为原料研究好氧发酵过程挥发性有机物（Volatile Organic Compound，VOCs）的产排特征及主要致臭物质，开展牛粪好氧发酵试验，采用气相色谱-质谱法分析测定发酵升温期、高温期、降温期及腐熟期等不同发酵阶段的VOCs组分和浓度，硼酸溶液吸收，盐酸滴定法测定NH3，便携式检测器（Tion NH3-H2S 300 G）测定H2S，3点比较式臭袋法测定不同发酵阶段臭气浓度。结果表明，牛粪好氧发酵过程中共检出31种VOCs，其中含硫化合物42种，醇类1种，酯类1种，酮类1种，卤代烃4种，苯系物9种，烷烃类8种，烯烃3种；在好氧发酵高温期臭气浓度最高为724（无量纲），VOCs产生与排放主要在高温期。基于恶臭污染排放标准和恶臭物质气味活度值，并结合各物质检出率、GS-MS图谱及相关性分析，发现NH3、H2S、甲硫醚是牛粪好氧发酵过程的主要致臭物质；其次芳香族化合物对臭气浓度贡献也相对较大，应进行重点监测与控制。该研究可为牛粪好氧发酵过程臭气物质减控提供理论支撑。     

猪粪好氧发酵过程中挥发性有机物组分分析及致臭因子的确定

为了控制猪粪好氧发酵中产生的挥发性有机物(volatile organic compounds)及主要致臭物质,开展了猪粪好氧发酵试验,通过连续监测猪粪好氧发酵过程中所排放的挥发性气体,研究猪粪好氧发酵中产生的VOCs组分及其致臭因子。研究表明,在猪粪好氧发酵过程中共产生33种挥发性物质,除氨气和硫化氢外,共有31种VOCs,包括芳香烃12种,醛类8种,硫醇硫醚类4种,卤代烃4种,酮类2种,胺类1种;猪粪好氧发酵中主要致臭物质为:二甲二硫、甲硫醚、二甲三硫、乙醛和硫化氢,并建议将甲硫醚作为猪粪好氧发酵中产生的恶臭污染指示物。该研究可为猪粪堆肥过程中恶臭物质的监测、制定控制策略提供参考。     

病死猪辅热好氧发酵尾气中的恶臭物质分析

为了明确病死猪辅热好氧发酵过程中产生的恶臭气体的种类及其排放规律,为控制恶臭气体排放浓度、降低病死猪无害化处理过程对环境的污染提供基础依据,该研究以病死猪为发酵原料,玉米秸秆为辅料,开展病死猪辅热好氧发酵试验,发酵过程中,采集处理槽排放的尾气,分析尾气中的有机恶臭物质组分并测定其排放浓度,同时测定其中的氨气浓度,并对不同发酵阶段尾气中气味活度值大于1的恶臭物质进行相关性分析和主成分分析。结果表明：在病死猪辅热好氧发酵过程中共检出36种恶臭物质,其中能准确定性与定量检测的有19种,包括3种含硫化合物,1种烷烃化合物,12种芳香烃化合物,1种酚类化合物,1种胺类化合物和1种无机气体;发酵全程或部分时间点超过其嗅阈值的有3-乙基甲苯、4-乙基甲苯、二甲基二硫醚、二甲基硫醚、氨气、对甲酚、甲硫醇、三甲胺8种,达到的最高浓度依次为0.241、0.350、0.247、0.280、69.06、0.041、0.314、0.033 mg/m3,与其嗅阈值的比值依次为2.745 7、8.634 7、29.325 6、36.981 5、66.669 1、173.314 5、374.77、432.471 1;各发酵阶段的主要致臭物质成分存在差异：在0～12 h的发酵阶段,三甲胺、甲硫醇、二甲基硫醚、二甲基二硫醚、氨气、对甲酚、3-乙基甲苯、4-乙基甲苯为主要致臭物质,在12～36 h的发酵阶段,三甲胺、甲硫醇、二甲基硫醚、二甲基二硫醚、氨气、对甲酚为主要致臭物质,在36～72 h的发酵阶段,三甲胺、甲硫醇、二甲基硫醚、二甲基二硫醚、氨气为主要致臭物质;不同发酵阶段的臭气强度存在较大波动：在0～72 h内的发酵过程中,0～3 h内臭气强度缓慢增强,但第6小时臭气强度有明显下降,在6～18 h时再次增强,第18小时臭气强度达到峰值,18～72 h内持续下降直至平稳。该研究可为病死猪辅热好氧发酵过程中恶臭物质的减控策略提供理论参考。     

生活垃圾堆肥过程中恶臭物质分析

恶臭污染已成为生活垃圾堆肥过程中的主要环境问题.以15~80 mm粒径段的生活垃圾作为研究对象,利用嗅觉测定法和GC-MS分析了不同阶段堆肥尾气的臭气浓度和恶臭化合物的种类及其排放浓度,并对不同堆肥阶段臭气浓度和恶臭物质排放浓度的相关性进行分析.结果表明,垃圾堆肥过程中共检测到50种挥发性有机物,其中含硫恶臭物质5种,烃类化合物25种,芳香烃类化合物14种,其他物质6种.通过相关性分析,发现硫化氢、甲硫醚、二硫化碳、二甲二硫、1,3二甲基苯和邻二甲苯均与臭气浓度呈极显著相关(p<0.01),结合各恶臭物质的嗅阈值,15~80 mm粒径段垃圾堆肥过程中恶臭物质优先控制的顺序为硫化氢>甲硫醚>二甲二硫>二硫化碳>1,3二甲基苯>邻二甲苯.甲硫醇的嗅阈值非常低,即使其排放浓度很低,也会带来严重的臭气污染;NH3虽然对臭气浓度的贡献相对较小,但是其排放量很大,因此也应该对这2种恶臭物质进行重点监测和控制.该研究结果为生活垃圾堆肥过程中恶臭物质的监测、制定控制策略提供参考.     

猪粪堆肥挥发性有机物的产生规律与影响因素

堆肥是畜禽粪便处理及资源化利用的有效途径,然而堆肥过程中极易产生挥发性有机物(VOCs,volatile organic compounds),引发恶臭问题,并对人体健康带来危害。该研究以猪粪和秸秆为原料,通过堆肥试验,研究了含水率、碳氮比和通风速率等工艺参数对猪粪堆肥过程中主要VOCs产生的影响。研究结果表明:堆肥过程中TVOCs的最高体积分数可达2 000×10~(-6)以上,主要在堆肥升温期产生。二甲二硫、二甲三硫是主要的致臭VOCs,其中,影响二甲二硫排放的主要因素为物料初始含水率,影响二甲三硫排放的主要因素为通风速率。极差及方差分析结果表明,堆肥过程中采用含水率65%,碳氮比30,通风速率0.1 m~3/(min·m~3)可以有效控制VOCs的排放。     

生物过滤法去除死猪堆肥排放臭气效果的中试

为研究生物过滤法去除死猪堆肥发酵处理过程产生臭气以及挥发性有机物(volatile organic compounds,VOCs)的可行性,开展了死猪和猪粪混合堆肥试验,分析了死猪堆肥过程臭气浓度特性和VOCs组分特征,对生物过滤法去除臭气中VOCs的工艺关键参数-停留时间进行优化试验。死猪堆肥过程中排放VOCs种类达37种,其中主要致臭组分为三甲胺、二甲基硫、二甲基二硫、二甲基三硫;以腐熟猪粪堆肥作为滤料(添加3%活性污泥),在停留时间为30~100 s的条件下,生物过滤法对死猪堆肥排放臭气去除率达90%以上;停留时间60~100 s的条件下对VOCs中主要致臭组分的去除效率达82.2%~100%,生物过滤法去除死猪堆肥过程臭气浓度和VOCs的优化停留时间为60 s。研究结果能为死猪堆肥发酵过程排放臭气的处理和控制技术进一步研发提供科学依据。     

风干预处理对堆肥腐熟度及臭气排放量的影响

该研究以风干猪粪堆肥为处理,以新鲜猪粪堆肥为对照,在秸秆调理相同C/N基础上,对两个处理腐熟度和臭气排放进行比较分析。从温度、p H值、电导率和发芽率来看,利用新鲜猪粪和风干猪粪堆肥所得的产品均能达到腐熟和无害化标准;在硫化氢、羰基硫、二硫化碳、甲硫醚、乙硫醚、二甲二硫、甲硫醇和乙硫醇几种含硫臭气中,甲硫醚和二甲二硫占96%以上;风干猪粪堆肥比新鲜猪粪堆肥少排放71.09%的氨气,66.11%的甲硫醚和9.66%的二甲二硫。在不考虑风干环节存在的问题条件下,与新鲜猪粪堆肥相比,风干猪粪堆肥堆肥时间短,在堆肥品质提高的基础上,堆肥产品产量增加60%。通过降低水分和体积风干猪粪运输成本降低1/3,且对环境影响小,是远距离资源化处理畜禽粪便的较好途径。     

畜禽粪含氮臭气成分的排放及其影响因素

氨和三甲胺是畜禽粪恶臭气体中的两种含氮臭气成分 ,畜禽粪排放的氨、三甲胺的体积分数分别达到1×10-6、0.02×10-6 时便可引起恶臭。畜禽粪在90d内的氨挥发量占粪便总量的0.007 %—0.354 %,其中以鸡粪最高、马粪最低。碳氮比、微生物以及化学物质和天然物质的添加物对畜禽粪含氮臭气成分的排放有直接影响。     

牛粪和玉米秸秆混合好氧堆肥过程分层规律

好氧堆肥过程常存在分层现象,对于发酵产物的均一性和整体质量存在影响。为探究好氧堆肥物料病原菌灭活的分层情况,该研究以不翻抛（T1）为对照组,设置3组好氧堆肥试验（T2高温期翻抛、T3降温期翻抛、T4高温期和降温期翻抛）,对牛粪好氧堆肥过程中常规理化性质和病原菌去除效率等进行分析,并利用克里格法（KRIGING）对堆体不同位置的温度和含水率进行插值分析。结果表明,4个处理发酵温度均达到了《畜禽粪便堆肥技术规范》要求,高温期最长的处理为T3和T4,达到7 d,T4处理的病原菌去除率最高,达到97.15%;从分层规律来看,堆体含水率从高到低为上层、中层、下层;好氧堆肥物料病原菌去除效率顺序从高到低为中层、下层、上层,4个处理病原菌去除率均不低于95.56%。综合考虑,高温期和降温期翻抛（T4处理）更有利于牛粪和秸秆混合堆肥物料整体实现无害化。该研究可为牛粪好氧堆肥过程中病原菌杀灭和翻抛参数的优化提供技术指导。     

农业有机废弃物发酵CO2施肥在大棚生产上的应用及其环境效应

利用作物秸秆与畜禽粪便发酵产生CO2的原理,设计了适合农业生产用的简易发酵装置。通过接种3种高效产气菌及堆料pH的调节,发酵大棚内CO2浓度可提高1倍以上,且一次堆料的发酵时间可维持3周左右。该农业有机废弃物发酵CO2施肥技术,可使大棚内的芹菜、生菜、莴苣、油麦菜和青菜5种蔬菜可食部分的生物量分别提高260%、135%、115%、140%和322%。因此,利用农业有机废弃物发酵进行大棚CO2施肥,不仅可以提高作物产量、增加农民收入,而且有望为农业固废合理处置提供新的策略。     

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.     

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.     

Enhanced establishment and growth of giant cardon cactus in an eroded field in the Sonoran Desert using native legume trees as nurse plants aided by plant growth-promoting microorganisms and compost

To evaluate the feasibility of long-term desert reforestation technology of mixed vegetation, cardon cactus (Pachycereus pringlei) seedlings from indoor and outdoor nurseries were planted in the field adjacent to one seedling of potential legume nurse trees: mesquite amargo (Prosopis articulata), yellow palo verde (Parkinsonia microphylla), and blue palo verde (Parkinsonia florida). Some of the planting holes were also supplemented with common dairy compost. Additionally, the combinations of legume tree–cactus were inoculated with either a consortium of desert arbuscular mycorrhizal (AM) fungi, plant growth promoting bacteria (PGPB; the diazotroph Azospirillum brasilense Cd, and the phosphate solubilizer Paenibacillus sp.), or a mixture of all. The field experiments were evaluated periodically during 30 months for survival and growth. Cardons reared in an outdoor screen house survived better in the field than those reared in a controlled growth chamber and hardened later outdoors. Association with any legume nurse tree increased survival and enhanced growth of untreated cardons. For cardons growing alone, application of either compost, AM fungi, and all the treatments combined increased survival. For these plants, no treatment affected plant growth during the first 3 months after transplanting. Later, all treatments, except for AM fungi, enhanced plant growth. However, only 2 years after transplanting the enhanced growth effect of AM fungi was also significant. In the presence of the legume nurse trees, transient positive effects on cardon growth were recorded. General evaluation after 30 months of cultivation showed that the treatments positively affected cardon growth when growing alone or in combination only with mesquite amargo but not with the other two legume trees. This study proposes that young legume trees have the capacity to enhance survival and growth of cardon cactus, depending on the legume cactus combination. Additional treatments such as compost or PGPB can either amplify the effect or else attenuate it.     

Karyotypic and genome size variation in Cajanus cajan (L.) Millsp. (pigeonpea) and some wild relatives

Detailed karyotypes and 4C DNA amounts have been studied in five cultivars of Cajanus cajan and 20 species belonging to Cajanus, Rhynchosia, Dunbaria, Flemingia and Paracalyx. C. cajan shows intraspecific variability and its karyotype is most similar to that of C. cajanifolius (sect. Cajanus) in the morphology and number of satellite chromosomes and the lack of any correlation between chromosome size within the complement and asymmetry. Karyotypes of C. lineatus and C. sericeus belonging to sect. Atylia are similar with respect to maximum r-index and the ratio of longest and shortest chromosomes in their respective complements. C. acutifolius (sect. Frutocosa) is distinct in having a very low ratio (1.44) between the longest and the shortest chromosomes, while in C. albicans, C. goensis, C. scarabaeoides (sect. Cantharospermum) there is no chromosome pair with r-index >2.0. C. mollis and C. volubilis (sect. Volubilis) show similarity with regard to ratio between the longest and the shortest chromosomes and a distinct chromosome pair with an arm ratio of 2.7 and C. platycarpus is distinct (sect. Rhynchosoides) in having the smallest ratio (1.36) between the longest and the shortest chromosomes. 4C DNA amounts in Cajanus and Rhynchosia vary between 3.28 pg to 11.69 pg and 4.92 pg to 11.13 pg respectively, while in Dunbaria, Flemingia and Paracalyx these vary between 4.70 and 7:06 pg. In the genus Cajanus karyotypic features and 4C DNA amounts agree with the sectional classification and bring out a close relationship between C. cajan and C. cajanifolius. This is supported by studies based on seed protein patterns, isozyme analysis, trypsin and chymotrypsin inhibitor patterns, RFLP and RAPD data and crossability relationships. A clear relation between DNA amount and abnormalities effecting the extent of pairing and recombination in interspecific hybrids shows the importance of this study in developing future breeding programme involving C. cajan and its wild relatives that are of potential value.     

Effect of some fungicide seed treatments on the survival of Bradyrhizobium japonicum and on the nodulation and yield of soybean [Glycine max. (L) Merr.]

Several commercial fungicide seed treatments were evaluated for their possible effect on the survival of Bradyrhizobium japonicum on seeds and on the nodulation and yield of soybeans in a greenhouse and a field experiment. quinolate Pro (carbendazim and oxine copper), Vitavax 200FF (carboxin and thiram), and Monceren (pencycuron) had a small effect or no effect on the survival of B. japonicum and on the nodulation and yield of soybeans. They can thus be considered compatible with soybean seed inoculation. Germipro UFB (carbendazim and iprodione), Apron 35J (metalaxyl), and Tachigaren (hymexazol) decreased B. japonicum survival and the nodulation and yield of soybeans and thus cannot be considered compatible with soybean seed inoculation.     

Einfluss der düngungsmethoden auf die entwicklung von zuckerrübenkrankheiten

Während neunjähriger (1994-2002) Untersuchungen in der Versuchsanstalt Ba?cyny (Fahlerde, Fall-Gleyboden, ausgebildet aus leichtem Lehmboden) wurde der Befall mit Krankheiten an der Zuckerrübe in Abhängigkeit von der Düngungsmethode bewertet. Folgende Methoden wurden angewendet: A - Mineraldünger, B - Stalldung und Mineraldünger, C - Stroh-, Gründung und Mineraldünger, D - Kompostdünger und Biopräparate (ökologische Düngung). Auf den Objekten A, B, C wurden bei konstanter Phosphor-Kalium-Düngung die Stickstoffgaben von 0 bis 180 kg.ha^?1 differenziert. Auf dem ökologischen Objekt D ohne Mineraldünger wurden statt Stickstoff die Biopräparate P₅₀₀ und P₅₀₁ verabreicht. Der geringste Befall von Krankheiten wurde an der Zuckerrübe auf jenem Objekt festgestellt, das mit Kompost und den Biopräparaten gedüngt worden war. Im Rahmen der konventionellen Düngungsmethoden wurde allgemein die höchste Intensität der Krankheiten an der mit Stroh, Gründung und Mineraldünger gedüngten Zuckerrübe beobachtet. Ausnahmen von dieser Regel bildete das Vorkommen von echtem Mehltau und Keimlingsfäule. Auf den Objekten A, B, C nahm die Intensität der Krankheiten mit der Steigerung der Stickstoffgabe zu. Auch die auf Objekt D verabreichten Biopräparate stimulierten die Entwicklung der Krankheiten. The effect of various fertilization methods on the diseases of sugar beet was estimated on the basis of nine-year studies (1994-2002) conducted in the Experimental Production Farm in Ba?cyny on loess-based, sedimentary-gley, light-clay soil. The following fertilization methods were applied: A - mineral fertilization, B - mineral and manure fertilization, C - straw, green manure and mineral fertilization, D - ecological compost and biodynamic preparations fertilization. In the objects A, B and C fertilized with phosphorus and potassium, various doses of nitrogen ranging from 0 to 180 kg/ha^?1 were used. In the ecological object D, where mineral fertilization was not used, biodynamic preparations P₅₀₀ and P₅₀₁ were applied instead of nitrogen. The lowest ratio of the diseases of sugar beet was observed in the object fertilized with the compost and biodynamic preparations. In view of the conventional fertilization methods, generally the highest incidence of diseases was noted in the sugar beet fertilized with straw, green manure and mineral fertilizers. The exception was the occurrence of powdery mildew and the black leg. In objects A, B and C the incidence of the diseases increased with the increase in nitrogen doses. The applied biodynamical preparations in the object D stimulated the development of diseases too.     

Prospects for control of Pythium damping-off of lettuce with Trichoderma,Gliocladium and Enterobacter spp.

Summary Damping-off of lettuce (Lactuca sativa) caused by Pythium ultimum was studied in pots containing a non-sterile potting mix in the glasshouse. Fifty P. ultimum sporangia g^-1 compost reduced the plant stand to 15% and shoot dry weight to 18%, but this reduction was totally prevented by applying Trichoderma harzianum at 2×10⁵ viable propagules g^-1 potting mix. Gliocladium virens and Enterobacter cloacae also alleviated the damping-off. E. cloacae did not adversely affect the action of the fungal antagonists. The co-existence of the bacterial and fungal antagonists was revealed on the root surface and inner surface of the testa by scanning electron microscopy, indicating the compatibility of the biocontrol agents.     

细菌、真菌及植物氮营养信号研究进展

氮素吸收代谢是所有生物生命活动的核心部分,因此,各种生物对氮的吸收与同化过程都有精细的调节。这种调节依赖于生物对体内氮素状况信号及体外（生长介质中）氮素信号的感受。过去几十年中,在细菌、真菌中已经对氮素营养信号有了较好的研究,而植物中则相对缓慢,但也有了一定的认识。本文重点比较细菌、真菌及植物中氮信号系统的组成,以期为进一步认识植物中的氮信号接受与转导系统提供启示。     

Potential of wild species for genetic enhancement of some semi-arid food crops

Discovery and incorporation of genes from wild species provide means to sustain crop improvement, particularly when levels of resistance in the cultigens are low and virulent strains of pests and pathogens overcome the host plant resistance. The extent of utilization and the potential of the wild genepool for genetic enhancement were reviewed in five important food crops viz. sorghum, pearl millet, chickpea, pigeonpea and groundnut grown in the semi-arid tropics. Introgression from compatible wild germplasm in the primary gene pool resulted in transfer of new cytoplasmic male sterility systems in pearl millet and pigeonpea, development of high protein, cleistogamous flower and dwarf pigeonpea lines and foliar disease resistant groundnut cultivars. Utilization of wild species in secondary and tertiary gene pools has been generally limited due to sterility, restricted recombination or cross incompatibility. Nevertheless, these species are extremely important as they contain high levels of resistance to several important biotic and abiotic stresses. Several of them, like those belonging to the Parasorghum section and the rhizomatous Arachis species are sources of multiple resistances and hold great promise to sustain crop productivity.     

“绿色革命”以来大气CO2浓度升高对C3作物营养品质的影响

自20世纪60年代"绿色革命"以来,育种技术和农耕技术的发展促进了农作物产量的大幅提升,然而作物的营养品质出现下降趋势。在相似的遗传背景下,大气CO_2浓度升高会使单位体积农作物产品的营养元素含量下降,因此"绿色革命"至今,农作物产品的营养元素下降可能受大气CO_2浓度升高影响。通过植物生长箱模拟"绿色革命"初期和目前的大气CO_2浓度水平(310μmol/mol和400μmol/mol),针对主要C_3作物水稻、小麦和大豆,研究"绿色革命"以来大气CO_2浓度升高对其籽粒的C、N、Fe、Zn元素含量的影响,结果表明:CO_2浓度升高对3种作物籽粒的C元素含量几乎没有影响,变化幅度在±1.5%之间;籽粒的N、Fe、Zn元素含量普遍呈现下降趋势,但均未达到显著水平。