How to overcome inter-electrode variability and instability to quantify dissolved oxygen, Fe(II), mn(II), and S(?II) in undisturbed soils and sediments using voltammetry

Background

Although uniquely capable of measuring multiple redox constituents nearly simultaneously with no or minimal sample pretreatment, voltammetry is currently underutilized in characterizing redox conditions in aquatic and terrestrial systems. Investigation of undisturbed media such as pore water requires a solid-state electrode, and such electrodes can be difficult to fabricate reproducibly. An approach to determine the concentrations of electroactive constituents using indirectly calibrated electrodes has been developed, but the protocol for and accuracy of this approach??the pilot ion method??has not been documented in detail.

Results

A detailed procedure for testing electrode quality is provided, and the application and limitations of the pilot ion method have been documented. To quantify Fe(II) and Mn(II), subtraction of non-linear baseline functions from voltammetric signals produced better calibration curves than did linear baselines, enabled lower detection limits and reliable deconvolution of overlapping signals, and was successfully applied to sediment pore water signals. We observed that electrode sensitivities often vary by tens of percent, and that the sensitivity declines over time. The ratio of calibration slopes of Mn(II) to Fe(II) varied by no more than 11% from one Hg/Au electrode to another and Fe(II) concentrations predicted by the Mn(II) pilot ion were, on average, 13% different from their actual values. However, concentration predictions by the pilot ion method were worse for less than 15???M Fe(II) (46% different on average). The ratio of calibration slopes of Mn(II) to S(?II) varied by almost 20% from one Hg/Au electrode to another, and S(?II) predicted concentrations were as much as 58% different from their actual values. These predictions of Fe(II) and S(?II) concentrations indicate that the accuracy of the pilot ion method depends on how independent calibration slope ratios are from the electrode used. At medium-to-high concentration for the ocean, naturally derived dissolved organic carbon did not significantly affect the baseline-corrected electrode response of Mn(II) and Fe(II), but did significantly affect the response of S(?II).

Conclusions

Despite their intrinsic variability, Hg/Au electrodes fabricated by hand can be used to quantify O₂, S(?II), Fe(II), and Mn(II) without calibrating every electrode for every constituent of interest. The pilot ion method can achieve accuracies to within 20% or less, provided that the underlying principle??the independence of slope ratios??is demonstrated for all voltammetric techniques used, and effects of the physicochemical properties of the system on voltammetric signals are addressed through baseline subtraction.     

成矿元素相态对地球化学异常识别的作用

为确定元素相态识别异常的作用,研究了斑岩铜矿Cu和热液铅锌矿床Zn的硫化物相、氧化物相和结合相组成。斑岩铜矿区,Cu以硫化物相和氧化物相为主,(w硫化物相Cu+w氧化物相Cu)/w结合相Cu≥21、(w硫化物相Cu+w氧化物相Cu)/w全量Cu≥96%,是矿化异常的标志。在铅锌矿区,背景区Zn的含量主要是结合相;在w(Zn)≥200×10-6异常地段,Zn主要是以硫化物相(包括氧化物相)存在,(w硫化物相Zn+w氧化物相Zn)/w全量Zn≥87%、(w硫化物相Zn+w氧化物相Zn)/w结合相Zn≥7时是有利的找矿地段,将是指示出露矿和隐伏矿的标志。     

Weakly nonlinear approximation of periodic flow in phreatic aquifers

Published frequency-domain solutions of periodic flow in aquifers apply strictly to mathematically linear systems that arise when aquifer diffusivity is assumed constant in space and time. This assumption can be invalid in phreatic aquifers that experience spatiotemporal variation in the free surface position and consequent variation in saturated thickness. A weakly nonlinear approach to formulating and solving periodic flow problems in the frequency domain can be applied in situations where conventional linearized approximations break down. The weakly nonlinear equations provide robust approximations of the true nonlinear response and require much less computational effort and time to solve than the full nonlinear problem. Nondimensional rules of thumb are presented for choosing between linear, weakly nonlinear and nonlinear solution strategies.     

The Sea Empress oil spill (Wales, UK): effects on Common Scoter Melanitta nigra in Carmarthen Bay and status ten years later

Carmarthen Bay, UK, regularly supports internationally important numbers (>16,000) of non-breeding Common Scoters Melanitta nigra. The spill of 72,000 tonnes of crude oil from the Sea Empress in 1996 affected birds both through direct mortality and likely pollution of key food resources. Numbers were greatly reduced following the spill, whilst changes in the distribution of birds within Carmarthen Bay suggested that potentially sub-optimal foraging zones were used. However, ten years after the incident, numbers of Common Scoter were no different to those recorded immediately before the spill. Compared to some other spills, rapid revival is evident. Numbers increased to pre-spill levels within three winters and distributional changes suggested a concurrent return to previously contaminated feeding areas, implying that the ecosystem had regenerated sufficiently to support its top predator. The importance of prolonged, standardised monitoring of bird numbers and distribution as indicators of ecological recovery from environmental damage is emphasised.     

Survey of PAH in low density residential stormwater ponds in coastal South Carolina: false dark mussels (Mytilopsis leucophaeata) as potential biomonitors

The distribution of PAHs was studied in sediment and false dark mussels, Mytilopsis leucophaeata, of three brackish stormwater retention ponds on Kiawah Island, a gated residential community and golf resort. Impervious surface in pond watersheds ranged from 5 to 30%. Sediment concentrations were lower than those found in other studies of suburban residential areas, and there were no significant differences among ponds or seasons. Mean summation operatorPAH(16) values for sediments in Ponds 67, 100, and 37 were 184.7+/-101.3ng g(-1), 67.5+/-26.0ng g(-1), and 84.3+/-75.5ng g(-1), respectively. Mussel summation operatorPAH(16) concentrations from Pond 67 in August (mean 734.5+/-148.1ng g(-1)), and from Pond 37 in December (mean 1115.1+/-87.7ng g(-1)), were significantly higher than other ponds. Mean summation operatorPAH(16) values for mussels in Ponds 67, 100, and, 37 were 555.9+/-219.7ng g(-1), 312.5+/-99.1ng g(-1) and 737.8+/-419.8ng g(-1), respectively. The mean biota-to-sediment ratio was 7.6+/-8.1. Isomer ratios generally suggested pyrogenic sources. False dark mussels are a promising indicator species for PAH contamination because they are abundant, easy to sample, bioaccumulate PAH profiles representative of the time-integrated sediment profiles, and their PAH levels are less variable than either stormwater or sediment samples.     

白银厂矿田折腰山海相火山岩型铜矿床地球化学异常特征

论述了白银厂矿田折腰山铜矿床的地质,地球化学特征,认为该矿床的主要指示元素是Ｃｕ,Ａｇ,Ａｓ,Ｓｂ,Ｈｇ,Ｐｂ,Ｚｎ,Ａｕ,Ｃｄ,Ｂａ,进而讨论了这些元素在区域,矿床的异常特征以及垂直分带规律,最后总结出矿床的地球化学异常模式。     

七里山金矿山的岩石地球化学异常评价与找矿

在七里山金矿区开展了面积性岩石地球化学测量,圈定了4个金异常,其中2个是已知矿的反映,另2个是新发现的金异常。同时研究了已知金矿体的岩石、矿石和异常的元素特征,确定了矿床的指示元素以及元素分带序列,由此建立了异常评价指标。并对4个金异常进行了评价,认为2个新发现的金异常均有良好的找矿前景,提交了验证孔位。经4号金异常进行钻孔验证,在深部见到了富的金矿体。此次化探工作证明该金矿还有隐伏矿体存在,也证明利用岩石裂隙地球化学方法在危机矿山寻找隐伏矿是非常有意义的。     

热磁技术确定矿床有效指示元素的试验与效果

针对找矿指标的有效性和找矿模型的普适性问题,研究引入热磁技术,以乌努格吐山铜矿和丰山洞铜矿为例,对比分析了土壤热磁组分与岩石、岩石热磁组分与黄铁矿的元素组合。试验表明,在确定成矿指示元素组合方面,土壤热磁组分是一种可行的介质,相比岩石具有更高的元素含量,可以挖掘出更多的异常信息;而岩石热磁组分与黄铁矿则具有一致的元素组合,比较而言,岩石热磁组分具有更宽的适用范围(如风化岩石)。作为一种人工方法分离组分,热磁组分弥补了岩石或黄铁矿等自然介质本身所固有的一些不足,为成矿指示元素的选择提供了一个新的研究平台;对于确定同一类型矿床有效指示元素组合,解决找矿模型的普适性问题,开拓了一种新思路。     

岩浆溶离型Cu—Ni硫化物矿床元素组合和地球化学评价指标

铜镍矿床的地球化学勘查评价实质上是基性－超基性岩体含矿性的评价。岩浆铜镍硫化物矿床与基性、超基性岩体具有空间和成因联系，其主要成晕微量元素以Cu、Ni、Co、Cr、Ag为主，而且含矿岩体的这些元素的平均值高、离差大。矿床区域地球化学异常发育，异常的分布受基性－超基性岩岩群和岩带制约，异常浓集中心与矿田的岩矿体一致。矿区异常继承了区域异常的组分，异常的高值区与矿床对应。矿床的原生晕具有组分分带，前缘元素是I、F、B、Ba、As、Mo；近矿元素是Ag、Cr；矿元素是Cu、Ni、Co。利用原生晕的组分分带特征可判断矿体的剥蚀程度和预测隐伏的岩矿体。     

西藏玉龙斑岩铜钼矿床区域地球化学异常特征和找矿标志

研究了西藏玉龙斑岩铜矿矿床的区域地球化学特征,结合地质条件综合分析了区域地球化学异常分布规律与矿床的关系,提出了地质、地球化学找矿标志。这对玉龙成矿带进一步勘查找矿有一定的意义。