A comparison of reliability of soil cadmium determination by standard spectrometric methods

Inductively coupled plasma emission spectrometry (ICP-OES) is the most common method for determination of soil Cd, yet spectral and matrix interferences affect measurements at the available analytical wavelengths for this metal. This study evaluated the severity of the interference over a range of total soil Cd by comparing ICP-OES and inductively coupled plasma mass spectrometry (ICP-MS) measurements of Cd in acid digests. Using the emission at 226.5 nm, ICP-OES was generally unable to quantify soil Cd at low (near-background) levels and gave unreliable values compared with ICP-MS. Using the line at 228.8 nm, a marked positive bias in Cd measurement (relative to the 226.5 nm measurement) was attributable to arsenic (As) interference even at soil As concentrations below 10 mg kg. This spectral interference in ICP-OES was severe in As-contaminated orchard soils, giving a false value for soil total Cd near 2 mg kg when soil As was 100 to 150 mg kg. In attempting to avoid these ICP emission-specific interferences, this study evaluated a method to estimate total soil Cd using 1 M HNO extraction followed by determination of Cd by flame atomic absorption (FAA), either with or without preconcentration of Cd using an Aliquat-heptanone extractant. The 1 M HNO extracted an average of 82% of total soil Cd. The FAA method had no significant interferences and estimated the total Cd concentrations in all soils tested with acceptable accuracy. For Cd-contaminated soils, the Aliquat-heptanone preconcentration step was not necessary, as FAA sensitivity was adequate for quantification of extractable soil Cd and reliable estimation of total soil Cd.     

Heavy metal distribution and chemical speciation in tailings and soils around a Pb-Zn mine in Spain

Soil pollution by lead, zinc, cadmium and copper was characterized in the mine tailings and surrounding soils (arable and pasture lands) of an old Spanish Pb-Zn mine. Sixty soil samples were analyzed, determining the total metal concentration by acid digestion and the chemical fractionation of Pb and Zn by the modified BCR sequential extraction method. Samples belonging to mine waste areas showed the highest values, with mean concentrations of 28,453.50 mg kg(-1) for Pb, 7000.44 mg kg(-1) for Zn, 20.57 mg kg(-1) for Cd and 308.48 mg kg(-1) for Cu. High concentrations of Pb, Zn and Cd were found in many of the samples taken from surrounding arable and pasture lands, indicating a certain extent of spreading of heavy metal pollution. Acidic drainage and wind transport of dust were proposed as the main effects causing the dispersion of pollution. Sequential extraction showed that most of the Pb was associated with non-residual fractions, mainly in reducible form, in all the collected samples. Zn appeared mainly associated with the acid-extractable form in mine tailing samples, while the residual form was the predominant one in samples belonging to surrounding areas. Comparison of our results with several criteria reported in the literature for risk assessment in soils polluted by heavy metals showed the need to treat the mine tailings dumped in the mine area.     

Metal bioavailability and speciation in a wetland tailings repository amended with biosolids compost,wood ash,and sulfate

Lead poisoning of waterfowl from direct ingestion of wetland mine tailings has been reported at the Coeur d'Alene River basin in Idaho. A greenhouse study was conducted to evaluate the effects of surface applications of amendments on lead bioavailability in the tailings. Treatments included sediment only, and sediment with three different surface amendments: (i) biosolids compost plus wood ash, (ii) compost + wood ash + a low SO4(2-) addition as K2SO4, and (iii) compost + wood ash + a high SO4(2-) addition. Measured variables included growth and tissue Pb, Zn, and Cd concentration of arrowhead (Sagittaria latifolia Willd.) and cattail (Typha latifolia L.) and soil pH, redox potential (Eh), pore water Pb, Pb speciation by X-ray absorption spectroscopy, and in vitro Pb bioavailability. The compost + ash amendment alleviated phytotoxicity for both plant species. Bioavailability of Pb as measured by a rapid in vitro extract decreased by 24 to 34% (over control) in the tailings directly below the amendment layer in the compost + SO4 treatments. The ratio of acid volatile sulfide (AVS) to simultaneously extracted metals (SEM) also indicated a reduction in Pb bioavailability (1:40 control, 1:20 compost, 1:8 compost + low SO4, and 1:3 compost + high SO4). Extended X-ray adsorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy data indicated that lead sulfide was greater after 99 d in the treatments that included additions of sulfate. These results indicated that, under reducing conditions, surface amendments of compost + wood ash (with or without sulfate) decreased the bioavailability of Pb in metal-contaminated mine tailings.     

硫酸锰催化法测定高氯根气田水化学需氧量

文章针对高氯根气田水特点,使用硫酸锰代替GB／T11914—1989《水质化学需氧量的测定重铬酸盐法》中的硫酸银作为催化剂,确定了硫酸锰催化法测定化学需氧量的试验条件。分别在4个实验室间开展比对测试,并对川西北气矿3个典型井站高氯根气田水开展现场应用,测定结果的相对偏差均在规定范围内,取得了良好的应用效果。     

Environmental assessment of mercury dispersion, transformation and bioavailability in the Lake Victoria Goldfields, Tanzania

Environmental dispersion and transformation of mercury discharged from gold mining operations has been investigated in field and laboratory studies in order to provide better understanding of the degree of mercury (Hg) pollution and bioavailability in the Lake Victoria goldfields (LVGF) ecosystems. This paper reviews results already published elsewhere and presents additional data on Hg dynamics in the LVGF. Studies conducted at the Mugusu and Rwamagaza artisanal mines indicated different degrees of Hg contamination and dispersion in environmental matrices. Mercury concentration in contaminated river sediments near the Mugusu mine varied from 6.0 to 0.5 mg/kg on a dry weight basis. The highest Hg contamination levels (165-232 mg/kg) were associated with mine tailings at the Rwamagaza mine. Mercury concentrations in fish representing different dietary habits on the southwestern shore of Lake Victoria at the Nungwe Bay were very low (2-35 microg/kg) and thought to represent background levels. These and other results suggested that the use of Hg in gold extraction in the LVGF has not caused high Hg levels in lake fish. The study of Hg in lichens showed Parmelia lichen to be an effective bioindicator for atmospheric Hg contamination due to Hg emissions from gold-amalgam firing and purification operations. The Hg levels in the lichens around the Mugusu mine ranged from 3.1 to 0.1 microg/g; the highest levels were recorded in the lichens sampled close to gold-amalgam processing sites. The regional background level in the Parmelia lichen was 0.05-0.10 microg/g, with a mean level of 0.07 microg/g. Studies of Hg transformation in the mine tailings revealed unexpectedly high methylmercury (MeHg) levels in the tailings (629-710 ng/g), which indicated that oxidation and methylation of metallic Hg in the tailings occurred at significant levels under tropical conditions. Re-equilibration of the tailings with freshwater (FW) indicated the MeHg was firmly bound in the tailings and therefore very little MeHg was released to the water column (0.2-1.5 ng/L). The methylation of Hg in tropical loamy clay soil contaminated with HgCl(2) (5 mg Hg/kg) yielded MeHg concentrations of 11 and 14 ng/g when inundated with seawater and FW, respectively, for 4 weeks. Little MeHg was transferred from the soil to the equilibrated water (< or = 0.4 ng/L). Atmospheric exposure of the soil pre-inundated with FW resulted in net degradation of MeHg during the 1st week of exposure, followed by net production and accumulation of MeHg in the soil (up to 15.5 ng/g) during atmospheric desiccation. Mercury uptake by fish from the Hg(0)-contaminated aquatic sediment-tailings system in the aquarium experiment was found to be low, suggesting the low availability of MeHg for bioaccumulation in the system. These and other results provide useful insights into Hg transformation, mobility and bioavailability in tropical aquatic systems affected by Hg pollution from gold mining operations.     

Field test of in situ soil amendments at the Tar Creek National Priorities List Superfund site

A range of soil amendments including diammonium phosphate fertilizer (DAP), municipal biosolids (BS), biosolids compost, and Al- and Fe-based water treatment residuals were tested on Pb-, Zn-, and Cd-contaminated yard soils and tailings at the Tar Creek NPL site in Oklahoma to determine if amendments could restore a vegetative cover and reduce metal availability in situ. For the yard soils, all amendments reduced bioaccessible (assessed with a physiologic-based extraction method) Pb, with reductions ranging from 35% (BS+Al, DAP 0.5%, DAP+Compost+Al) to 57% (Compost+Al). Plant Zn (Cynadon dactylon L.) and NH4 NO3-extractable Cd and Zn were also reduced by a number of amendments. For the tailings, all amendments excluding BS reduced bioaccessible Pb, with the largest reductions observed in the DAP 3% and DAP3%+BS treatments (75 and 84%). Plant growth was suppressed in all treatments that contained DAP for the first season, with the highest growth in the treatments that included compost and biosolids. In the second year, growth was vigorous for all treatments. Plant Zn and Cd and extractable metal concentration were also reduced. A number of treatments were identified that reduced bioaccessible Pb and sustained a healthy plant with reduced metal concentrations. For the yard soil, Compost+Al was the most effective treatment tested. For the tailings, BS+DAP 1% was the most effective treatment tested. These results indicate that in situ amendments offer a remedial alternative for the Tar Creek site.     

固相萃取-超高效液相色谱-串联质谱法测定地表水中5种磺胺类抗生素

建立了固相萃取-超高效液相色谱-串联质谱对水中5种磺胺类抗生素的测定分析方法。将水样经固相萃取后进样,经ACQUITY UPLC BEH C18(2.1 mm×100 mm,1.7μm)分离后,采用串联质谱电喷雾电离(ESI+),多反应监测(MRM)模式检测,内标法定量。方法的线性范围为5.0~100.0μg/L,线性相关系数均大于0.995,样品100倍浓缩后,检出限低至0.009μg/L;在5.0~100.0μg/L范围内,高中低3个水平的加标回收率为80.2%~90.7%,相对标准偏差(RSD)为4.3%~12.0%。该方法能够满足《国务院关于印发水污染防治行动计划的通知》限制使用抗生素等化学药品开展专项整治的需要,是一种高效、准确、灵敏度高的方法。     

甘肃党参中蛋白质的提取分析

实验采用盐溶法提取甘肃党参中蛋白质,用饱和(NH4) 2SO4溶液进行分级盐析、透析、浓缩后用SDS- PAGE分析,测定不同提取液中主要蛋白质的分子量.结果表明,用pH为6.0的PB缓冲液提取并用饱和度在60％以上的(NH4)2SO4溶液盐析时蛋白提取效果最好;经SDS- PAGE电泳后,初步鉴定出所提取党参蛋白质亚基中最大分子量为68885Da,最小分子量为15570Da.     

Comparison of Four <Emphasis Type="Italic">Sesbania</Emphasis> Species to Remediate Pb/Zn and Cu Mine Tailings

A 6-month greenhouse pot trial was performed, aimed at screening appropriate Sesbania species for remediation of Pb/Zn and Cu mine tailings. Performances of young seedlings of four Sesbania species (S. cannabina, S. grandiflora, S. rostrata, and S. sesban) were compared with and without inoculation of rhizobia. Seedlings were planted in two types of tailings amended with garden soil or garden soil mixed with river sediment. The results indicated that inoculated plants generally produced a higher biomass than samples without inoculation. Pb/Zn mine tailings containing rather high concentrations of total and water-soluble Cu, Pb, and Zn were toxic to plant growth compared with Cu mine tailings, according to the growth performance of the four species. Sesbania sesban and S. rostrata showed superior growth performance, compared to the other two species. Thus, they can serve as pioneer species to modify the barren environment, by providing organic matter and essential nutrients such as nitrogen, upon decomposition, in a relatively short period of time. This is especially true for S. rostrata, which is an annual plant that forms both stem and root nodules. However, a longer-term field trial should be conducted to investigate if superior species can beneficially modify the habitat for the growth of subsequent plant communities.     

铁尾矿路用对土壤环境质量影响及安全修复研究

为分析铁尾矿路用对道路沿线土壤环境质量影响的程度,对铁尾矿化学成分及有害物质进行测定,以秦巴山区的山地黄棕壤作为道路建设的耕土环境,把铁尾矿按70％～90％的推荐比例掺入,铁尾矿中的重金属按照最不利的全浸入式扩散进行分析,对黄棕壤中重金属含量超过限制要求的重金属进行安全修复,使铁尾矿道路沿线黄棕壤的重金属含量满足限制要...     

Degradation of biomacromolecules during high-rate composting of wheat straw-amended feces

Pig (Sus scrofa) feces, separately collected and amended with wheat straw, was composted in a tunnel reactor connected with a cooler. The composting process was monitored for 4 wk and the degradation of organic matter was studied by two chemical extraction methods, 13C cross polarization magic angle spinning (CPMAS) nuclear magnetic resonance (NMR) and pyrolysis gas chromatography-mass spectrometry (GC-MS). Wet-chemical extraction methods were not adequate to study the degradation of specific organic compounds as the extraction reagents did not give selective separation of hemicellulose, cellulose, proteins, and lignins. A new method was proposed to calculate the contribution of four biomacromolecules (aliphatics, proteins, polysaccharides, and lignin) from the 13C CPMAS NMR spectrum. Pyrolysis GC-MS allowed identification of the composition of the biomacromolecules. The biomacromolecules showed different rates of degradation during composting. High initial degradation rates of aliphatics, hemicellulose, and proteins were observed, where aliphatics were completely degraded and hemicellulose and proteins were partly recalcitrant during the four weeks of composting. The degradation rate of cellulose was much lower and degradation was not completed within the four weeks of composting. Lignin was not degraded during the thermophilic stage of composting but started to degrade slowly during the mesophilic stage. A combination of 13C CPMAS NMR and pyrolysis GC-MS gave good qualitative and semiquantitative assessments of the degradation of biomacromolecules during composting.     

PHOSPHORUS LOSSES FROM CROPLAND AS AFFECTED BY TILLAGE SYSTEM AND FERTILIZER APPLICATION METHOD1

ABSTRACT: A rainfall simulator was used to study the effectiveness of no-till and fertilizer application method on reducing phosphorus (P) losses from agricultural lands. Simulated rainfall was applied to 12 experimental field plots, each 0.01 ha in size. The plots were divided into no-till and conventional tillage systems. Two fertilizer application methods, subsurface injection and surface application, were investigated for the two tillage systems. Phosphorus fertilizer was applied at a rate of 46 kg/ha, 24 to 48 hours before the start of rain simulation. Water samples were collected from the base of each plot and analyzed for sediment and P content. No-till was found to be very effective in reducing runoff and sediment losses. No-till reduced sediment loss and total runoff volume by 92 and 67 percent, respectively. Subsurface injection of fertilizer, as compared to surface application, reduced PO₄ losses by 39 percent for no-till and by 35 percent for conventional tillage. The effect of tillage system on PO₄ losses was not significant. Reductions in total-P (P_T) losses due to no-till compared to the conventional tillage system were 89 and 91 percent for surface application and subsurface injection methods, respectively. Averaged across all fertilizer treatments, an equivalent of 0.9 and 8.9 percent of the P applied to the plots were lost from the no-till and conventional tillage plots, respectively.     

中药川附子非金属元素分析

本文论述了川附子非金属元素的分析：用ICP—AES法测定S、P和Si；离子色谱法测定Cl、S、P；极谱法和HG—AFS法测定痕量砷；ICP—AES和荧光法测定硒；GB法测定氯、氟和碘。应用提出的方法弄清了川附子用传统工艺食盐-胆巴混合溶液炮制前后非金属元素的含量与浓度变化，从而为中药化学成分进一步研究增添新内容一非金属元素及检测方法。     

宜宾兴文县僰王山镇水田土壤中硒形态分布特征及研究

为了客观分析土壤中硒形态分布特征及硒有效性影响因素,依据硒不同形态下的溶解度不同,采用四步五态连续浸提取技术,由弱到强的选择顺序提取僰王山镇水田土壤中硒的水溶态、可交换态、有机质结合态、硫化物/硒化物态、残渣态这5种形态,并用原子荧光光谱法分析和氢化物发生-原子荧光光谱法测定了土壤样品中5种形态硒和总硒的含量。初步总结了研究区水田土壤硒含量特征和硒形态分布特征。研究结果发现,僰王山镇水田土壤总硒含量变化范围为0.51~0.93 mg/kg,平均值0.714 mg/kg,远远超过全国土壤总硒平均值0.290 mg/kg,且超过了目前认为的富硒土壤的标准值0.4 mg/kg。从土壤中5种形态分析结果所占比例来看,有机质结合态和硫化物/硒化物态硒是硒元素的主要赋存形态,两者占土壤总硒含量的54.63%,反应了研究区土壤中硒富集与有机质结合态存在密切关系。     

环境监测中仪器分析方法不确定度的评估(Ⅱ)——原子吸收光谱分析中的测量不确定度

通过对环境样品分析中常用的原子吸收光谱法测量不确定度分量的分析,探讨了原子吸收光谱法测量不确定度的评估方法,针对不同环境基体样品、不同测定组分以及不同前处理方法的扩展不确定度进行了评定。原子吸收光谱分析中的测量不确定度主要来源于样品称量、消化液定容、仪器漂移及由吸收值通过标准曲线拟合求浓度部分,其中最主要的分量是由吸收值通过标准曲线拟合求样品溶液浓度时引起的测量不确定度。     

Selection of a water-extractable phosphorus test for manures and biosolids as an indicator of runoff loss potential

The correlation of runoff phosphorus (P) with water-extractable phosphorus (WEP) in land-applied manures and biosolids has spurred wide use of WEP as a water quality indicator. Land managers, planners, and researchers need a common WEP protocol to consistently use WEP in nutrient management. Our objectives were to (i) identify a common WEP protocol with sufficient accuracy and precision to be adopted by commercial testing laboratories and (ii) confirm that the common protocol is a reliable index of runoff P. Ten laboratories across North America evaluated alternative protocols with an array of manure and biosolids samples. A single laboratory analyzed all samples and conducted a separate runoff study with the manures and biosolids. Extraction ratio (solution:solids) was the most important factor affecting WEP, with WEP increasing from 10:1 to 100:1 and increasing from 100:1 to 200:1. When WEP was measured by a single laboratory, correlations with runoff P from packed soil boxes amended with manure and biosolids ranged from 0.79 to 0.92 across all protocol combinations (extraction ratio, filtration method, and P determination method). Correlations with P in runoff were slightly lower but significant when WEP was measured by the 10 labs (r=0.56-0.86). Based on laboratory repeatability and water quality evaluation criteria, we recommend the following common protocol: 100:1 extraction ratio; 1-h shaking and centrifuge 10 min at 1500xg (filter with Whatman #1 paper if necessary); and determining P by inductively coupled plasma-atomic emission spectrometry or colorimetric methods.     

Disturbance of water-extractable phosphorus determination by colloidal particles in a heavy clay soil from the Netherlands

Water extraction methods are widely used to extract phosphorus (P) from soils for both agronomic and environmental purposes. Both the presence of soil colloids in soil water filtrates, and the contribution of colloidal P to the molybdate-reactive phosphorus (MRP) concentration measured in these filtrates, are well documented. However, relatively little attention has been given to the direct disturbance by colloids of MRP measurement. The objective of this paper is to show this influence found for water extracts with a soil to solution ratio of 1:60 (v/v) (P(w)), obtained from a heavy clay soil in the Netherlands. Colloidal particles, which passed a 0.45-mum filter, caused a large overestimation of MRP. The low ionic strength of the P(w) filtrates (on average 0.64 mmol(c) L(-1)) probably caused soil dispersion and increased detachment of colloids from soil during extraction. After NaCl addition, followed by 0.45-mum filtration, MRP was on average 93% lower. This can be ascribed to flocculation of colloids and removal by filtration. A low ionic strength can thus lead to the direct disturbance by colloidal particles of MRP measurement in waters from soils sensitive to release of colloids.     

氯仿稀释法测定高浓度含酚废水

4-AAP萃取分光光度法测定挥发酚方法中，当挥发酚浓度超出校准曲线范围时，一般将水样稀释后重新分析测定。本文采用氯仿稀释萃取液测定吸光度，通过公式换算求得挥发酚浓度，试验表明，该方法准确可靠，操作简便快捷。     

Comparing Onsite and Offsite Methods for Measuring Norms for Trail Impacts

This study examined the comparability of onsite and offsite methods for measuring norms for trail impacts using photo/survey techniques. A total of 449 subjects participated in a study of Mudeung-Mountain Provincial Park, Gwang-Ju, Korea. For the overall photo evaluation method (OPEM), respondents rated the acceptability of bare soil area for each of a series of photographs. For the specific photo evaluation method (SPEM), respondents selected a photograph that illustrated the largest acceptable proportion of bare soil area from a series of 10 photographs. Overall, there were no substantial differences in maximum acceptable impacts between onsite (onsite-I visitor group surveyed at the actual trail points and onsite-II departing visitor group surveyed at the exit area) and offsite (students surveyed in a laboratory setting) groups for the two norm measurement alternatives (OPEM and SPEM). Subjects’ difficulty ratings were low for both methods, and there were no substantial differences in norms between individuals with high and low levels of experience at the park. The offsite method appears to be substitutable for onsite methods in this particular study area, which is a frontcountry setting with a relatively simple range of recreation opportunities. Implications and further studies are discussed.     

Barley, a potential species for initial reclamation of saline composite tailings of oil sands

The oil sands industry in Alberta (Canada) has developed the composite tailings (CT) process to reduce the fluid fine tails resulting from the processing of oil sands. This process uses a chemical coagulant (gypsum or alum) to produce aggregated fines (clay), so they are retained with the coarse sand fraction of the extraction tailings to form CT, from which fines-free water is released relatively quickly compared with untreated tailings. The resulting CT and CT waters are saline-sodic, with Na+, SO4(2-), and Cl- being the dominant ions. When freshly deposited, the CT deposits are too soft for access by reclamation equipment, and the time required for these deposits to remove the water sufficiently to support traffic is uncertain. A greenhouse study was designed to determine the suitability of barley (Hordeum vulgare L.) for reclamation of fresh CT deposits and to evaluate benefits of peat amendments. This study assessed germination, early plant growth, chlorophyll content, and survival of barley growing in alum- and gypsum-treated CT, with and without peat amendment. Ion and trace metal accumulation in the root and shoot tissues of barley was determined. Amendment of CT with peat improved germination, survival, and growth of barley, but did not prevent leaf injury (probably due to Na and Cl- and possibly multiple nutrient deficiency). Field studies will be undertaken to validate our greenhouse results suggesting that barley could be used to improve dewatering of the freshly deposited substrates, reduce soil erosion, and facilitate leaching of ions by root penetration into the substrate.