Distribution and Fractionation of Copper in Soils of Apple Orchards (5 pp)

Background Frequent application of Bordeaux mixture, which includes copper, as a fungicide in fruit and grape orchards may lead to copper accumulation in the soil, especially when orchard age and application times increase. The objectives of this study were: (i) to investigate the copper content and its spatial distribution in orchard soils; (ii) to identify the copper fractionation in soil and its relationship with plant uptake; (iii) to understand the characteristics of copper contamination in orchard soils. Materials and Methods Soil profile samples were taken in apple orchards with ages of 0, 5, 10, 20, 30 years and pot experiments were also carried out to study the effects of external copper input on copper fractionation. All soil samples were air-dried, ground and extracted with 0.43 mol L–1 HNO3 for the total absorbed copper. Fractionation determination was conducted following Tessier and Shuman sequential extraction methods, and copper was measured with AAS. Plant samples were first dry ashed, dissolved with 6 mol L–1 HCl and then copper and other elements were measured with ICP-MS.Results and Discussion Soil total Cu was higher in the apple orchards than that in non-orchard fields and was seen to have increased with orchard age. Soil Cu increased substantially with the average annual copper increase, ranging from 2.5 to 9 mg Cu kg–1. The distribution of copper in the soil profile was uneven, decreasing from surface to deeper layers, and the differences were significant, but the contents in every layer were also significantly correlated with those in the next layers. For all copper fractions, the organically bound, crystalline Mn oxide bound, and amorphous Fe bound fractions extracted with the Shuman method were much higher than the exchangeable and residual fractions. Using the Tessier method, organically bound, carbonate bound and Fe-Mn oxide bound fractions were much higher. With an increase in external copper input, the organically bound, crystalline Mn oxide bound and amorphous Fe bound fractions in the Shuman method and organically bound, carbonate bound and Fe-Mn oxide bound fractions in the Tessier method all increased significantly, while the changes in other fractions were not significant. Soil total copper and copper fractions were found to have good correlations with apple tree uptake. Copper in fruit flesh had significant correlations with soil total content in the 0–10 cm layer, all the copper fractions in the 0–5 cm layer, and some fractions in the deeper layers. Conclusion Copper content in orchard soils increased significantly with intensive application of Bordeaux mixtures and orchard age. Copper content decreased sharply from the topsoil to deeper soil layers. The copper contents in different layers also significantly correlated with those in the next layers. Dominant fractions of the copper in soil were mainly associated with organic matter, iron and manganese oxides and carbonates. A close relationship was found between the copper content in soils and in apple tree organs (which contained 8.9 to 66mg kg–1 Cu). Recommendation and Perspective Though most copper in the soil was specifically adsorbed or immobilized, and copper was mainly distributed in topsoil, which was essentially devoid of roots, the copper concentration of fruit still had significantly positive correlations with soil copper and most copper fractions. Therefore, measures must be taken to control copper accumulation in orchard soils and to make the apple fruit production sustainable.     

Assessing microbial degradation of o-xylene at field-scale from the reduction in mass flow rate combined with compound-specific isotope analyses

In recent years, natural attenuation (NA) has evolved into a possible remediation alternative, especially in the case of BTEX spills. In order to be approved by the regulators, biodegradation needs to be demonstrated which requires efficient site investigation and monitoring tools. Three methods--the Integral Groundwater Investigation method, the compound-specific isotope analysis (CSIA) and a newly developed combination of both--were used in this work to quantify at field scale the biodegradation of o-xylene at a former gasworks site which is heavily contaminated with BTEX and PAHs. First, the Integral Groundwater Investigation method [Schwarz, R., Ptak, T., Holder, T., Teutsch, G., 1998. Groundwater risk assessment at contaminated sites: a new investigation approach. In: Herbert, M. and Kovar, K. (Editors), GQ'98 Groundwater Quality: Remediation and Protection. IAHS Publication 250, pp. 68-71; COH 4 (2000) 170] was applied, which allows the determination of mass flow rates of o-xylene by integral pumping tests. Concentration time series obtained during pumping at two wells were used to calculate inversely contaminant mass flow rates at the two control planes that are defined by the diameter of the maximum isochrone. A reactive transport model was used within a Monte Carlo approach to identify biodegradation as the dominant process for reduction in the contaminant mass flow rate between the two consecutive control planes. Secondly, compound-specific carbon isotope analyses of o-xylene were performed on the basis of point-scale samples from the same two wells. The Rayleigh equation was used to quantify the degree of biodegradation that occurred between the wells. Thirdly, a combination of the Integral Groundwater Investigation method and the compound-specific isotope analysis was developed and applied. It comprises isotope measurements during the integral pumping tests and the evaluation of delta13C time series by an inversion algorithm to obtain spatially integrated mean isotope values at the control planes. It was shown that the Rayleigh equation is applicable to spatially integrated mean isotope values in order to obtain the mean biodegradation between the consecutive control planes. All three approaches yielded consistently a 98-99% degradation of o-xylene.     

水体溶解性有机物的化学分级表征:原理与方法

综述了水体溶解性有机物(DOM)的化学分级表征法即树脂吸附分级法(RA)的研究与进展,同时基于该方法存在的一些问题结合我国典型水质体系,从树脂的选择、净化、分级的定义、水样过柱流速、水样树脂体积比的确定等方面进行了研究探讨,给出了完整的实验参数和操作方法.     

土壤重金属化学形态的生物可利用性评价

重金属化学形态是近年来土壤化学、植物营养和环境科学研究领域的一个热点和难点,利用重金属的化学形态分布和含量变化来评价重金属的生物可利用性,有利于全面研究重金属的危害性和治理重金属污染土壤。结果表明,水溶态和交换态的重金属易被生物吸收利用,而残留态重金属一般不被生物利用,其它形态如碳酸盐结合态、铁锰氧化物结合态和有机物结合态的生物可利用性主要取决于外界环境的变化。     

水杉凋落物分解过程中溶解性有机质的分组组成变化

采用XAD-8树脂分组的方法研究水杉凋落物降解过程中DOM的含量及其组成的变化。结果表明，培养35天后DOC含量达到稳定值，而其组成仍未稳定。在整个培养过程中，HOA和HIM含量有明显变化；HON含量呈缓慢增加的趋势；AIM和HOB含量则没有明显变化。凋落物淋滤液DOM与表层土壤DOM组成相似，是土壤DOM的主要来源。土壤DOM中的AIM不是来源于凋落物淋滤液，而是主要来源于土壤腐殖质、根系分泌物等其它物质。     

黑柱石和水之间氢同位素平衡分馏的实验研究

在750-250℃温度范围内,对黑柱石-水之间的氢同位素平衡分馏进行了实验研究。研究中改进了氢同位素交换实验方法,从而保证了精度。研究结果表明,750-550℃温度范围内,黑柱石一水的分馏系数10~3lnα°_(黑柱石-水)=-30.51 10~6/T~2-59.86,550-350℃温度范围内,10~3lnα°_(黑柱石-水)与温度1/T~2间无依赖关系,其值为-105.0±0.7,.250℃时,交换率太低。文中讨论了黑柱石-水之间氢同位素分馏系数与温度、矿物晶体结构、矿物化学组成的关系及其地质意义。     

盐城凹陷凝析油地球化学特征

运用碳同位素、气相色谱、色谱 质谱、流体包裹体技术 ,研究了盐城凹陷凝析油地球化学特征 ,并与永安凹陷永 7井凝析油、下扬子海相原油进行了对比。该凝析油碳同位素为 -2 8 8‰～ 3 0 5‰ ,全油色谱中含有一定的长链正构烷烃 ,Pr/Ph为 1 5 6,三环萜烷含量高 ,伽玛蜡烷含量低 ,重排甾烷含量高 ,C2 9甾烷 >>C2 7甾烷 >C2 8甾烷。石蜡指数、庚烷值表明原油为高成熟凝析油 ,甲基菲指数MPI表明原油为未熟—低熟原油 ,C2 9甾烷 2 0S/ (2 0S+2 0R)值表明原油为成熟原油。这种成熟度的差异可能与不同成熟度原油的混合作用有关。油气主要充注时间为 6～ 1 5Ma。凝析油的主体可能源于泰州组烃源岩 ,凝析油的形成与蒸发分馏作用密不可分     

南京地区土壤沉积物中重金属形态研究

对南京地区４个环境单元－－公路干线，金属冶炼厂，大型生活垃圾场和江河滩涂土壤沉积物中重金属元素化学形态进行了分级提取实验研究。结果表明，有效态中，Ｃｕ以有机态为主，Ｐｂ以交换态为主，Ｃｏ、Ｍｎ以铁锰氧化物态为主，Ｆｅ、Ｎｉ有效态均小于其总量的１０％，并主要集中在铁锰氧化物态中，以大气为传播媒介的重金属人为叠加沉积（公路、工厂）其铁锰氧化物态含量相对较多，以水为传播媒介的重金属人为叠加沉积（垃圾场、     

南方天然水体DOM的化学分级、变化特征及三卤甲烷生成势(THMFP)特性研究

采用XAD树脂吸附法,在春季内(3～5月)连续对南方深圳水库中的水体溶解性有机物(DOM)进行化学分级表征.结果表明,天然水体DOM的总量和单个化学分级组分含量在一个季节会发生一定的波动,但总的分布特征在季节内未发生根本变化,即憎水酸(HoA)和亲水部分(HiM)浓度始终较高,而憎水碱(HoB)、憎水中性物(HoN)、弱憎水酸(WHoA)浓度则相对较低.同时,选取代表性时间点对DOM各化学分级组分进行了消毒副产物三卤甲烷生成势(THMFP)的研究,发现三卤甲烷(THMs)的主要前驱物为憎水和弱憎水有机部分,对THMFP的贡献共占约80%.进一步研究发现,憎水中性物、憎水酸、弱憎水酸的THMs生成能力较强,总体上与紫外吸收能力基本一致;但弱憎水酸表现略有不同,其SUVA(100×UV254/DOC)值并不十分突出,但三卤甲烷生成能力却明显较高,说明DOM的紫外吸收特性不能完全作为THMFP特性的替代指标.亲水物质(HiM)的SUVA值也不高,但其THMs生成能力接近憎水酸部分,值得水处理工艺研究重点关注.     

Pb和Cd赋存形态与土壤理化性质相关性研究

选择我国14种具有代表性的重金属污染土壤,测定其主要理化性质（pH、阳离子交换量、有机质、粉粒和黏粒）,采用改进的BCR顺序提取法对其中的Pb和Cd进行形态分析,运用SPSS 20.0软件进行Pearson相关性分析,建立逐步回归模型,研究重金属赋存形态与理化性质的相关性。结果表明,Pb和Cd的酸可溶态与pH值呈极显著负相关,相关性系数r分别为-0.80和-0.78,与阳离子交换量呈显著正相关,r分别为0.54和0.61,与有机质、粉粒和黏粒无相关性;Cd的可还原态与有机质呈显著正相关,r=0.56,与其它理化性质无相关性;可氧化态与有机质和黏粒呈显著正相关,与其它理化性质无相关性;残渣态与主要理化性质均无显著相关性。由逐步回归模型发现,酸可溶态、可还原态、可氧化态与理化性质回归效果均较好。