Perchlorate retention and mobility in soils

Adsorption and release of perchlorate in a variety of soils, minerals, and other media were studied when the solid media were exposed to low and high aqueous solutions of perchlorate salts. Low level ClO4- exposure was investigated by subjecting triplicate 5.0 g portions of a solid medium (38 different soils, minerals, or dusts) to 25 mL of an aqueous ammonium perchlorate (NH4ClO4) solution containing 670 ng mL(-1) (6.8 microM) perchlorate. This corresponds to a perchlorate-to-soil ratio of 3.4 microg g(-1) (34 nmol g(-1)). At this level of exposure, more than 90% of the perchlorate was recovered in the aqueous phase, as determined by ion chromatography. In some cases, more than 99% of the perchlorate remained in the aqueous phase. In some cases, the apparent loss of aqueous perchlorate was not clearly distinguishable from the variation due to experimental error. The forced perchlorate anion exchange capacities (PAECs) were studied by soaking triplicate 5.0 g portions of the solid media in 250 mL of 0.20 M sodium perchlorate (NaClO4) followed by repeated deionized water rinses (overnight soaks with mixing) until perchlorate concentrations fell below 20 ng mL(-1) in the rinse solutions. The dried residua were leached with 15.0 mL of 0.10 M sodium hydroxide. The leachates were analyzed by ion chromatography and the perchlorate concentrations thus found were subsequently used to calculate the PAECs. The measurable PAECs of the insoluble and settleable residua ranged from 4 to 150 nmol g(-1) (micromol kg(-1)), with most in the 20-50 nmol g(-1) range. In some soils or minerals, no sorption was detectable. The mineral bentonite was problematic, however. Overall, the findings support the widely accepted idea that perchlorate does not appreciably sorb to soils and that its mobility and fate are largely influenced by hydrologic and biologic factors. They also generally support the idea that intrasoil perchlorate content is depositional rather than sorptive. On the other hand, sorption (anion replacement) of perchlorate appears to occur in some soils. Therefore, the measurement of perchlorate in soils requires accounting for ion exchange phenomena; leaching with water alone may give inaccurate results. If perchlorate anion exchange is confirmed to be negligible, then leaching procedures may be simplified accordingly.     

离子色谱法-抑制型电导检测城市污水中的高氯酸根

利用离子色谱法-抑制型电导检测了城市污水中的持久污染物高氯酸根,以IonPac AS20高容量强亲水阴离子交换柱分离,NaOH流动相等度淋洗,高氯酸根在12min内出峰。高氯酸根在0.01~50 mg/L内具有良好的线性,相关系数为0.9998,50μl进样时检出限可达到3μg/L。方法可用于多种城市污水中高氯酸根的监测,样品测定的标准相对偏差在0.60%~0.94%之间,加标回收率在97.3%~105.8%之间,具有较好的准确性和重现性。     

Accumulation of perchlorate in tobacco plants: development of a plant kinetic model

Previous studies have shown that tobacco plants are tolerant of perchlorate and will accumulate perchlorate in plant tissues. This research determined the uptake, translocation, and accumulation of perchlorate in tobacco plants. Three hydroponics growth studies were completed under greenhouse conditions. Depletion of perchlorate in the hydroponics nutrient solution and accumulation of perchlorate in plant tissues were determined at two-day intervals using ion chromatography. Perchlorate primarily accumulated in tobacco leaves, yielding a substantial storage capacity for perchlorate. Mass balance results show that perchlorate degradation was negligible in plants. Tobacco plants were shown to effectively accumulate perchlorate over a wide range of initial concentrations (10 ppb to 100 ppm) from the hydroponics solution. Results suggest that plants are potential plants for the phytoremediation of perchlorate. A mathematical model was developed to describe the distribution of perchlorate in tobacco plants under rapid growth conditions. The Plant Kinetic (PK) model defined a plant as a set of compartments, described by mass balance differential equations and plant-specific physiological parameters. Data obtained from a separate hydroponics growth study with multiple solution perchlorate concentrations were used to validate predicted root, stem, and leaf concentrations. There was good agreement between model predictions and measured concentrations in the plant. The model, once adequately validated, can be applied to other terrestrial plants and inorganic chemicals currently used for both phytoremediation and ecological risk assessment.     

废水中微量Cr^6＋测定中的试样前处理

采用离子交换树脂预处理工业废水方法测定微量Ｃｒ＾６＋，排除了Ｃｒ＾３＋、Ｆｅ＾３＋、Ｈｇ＾２＋等阳离子干扰，减除水中浊度、色度、免去冗长预处理手续，使原方法简便易行，回收率达９０％以上。     

Monitoring perchlorate exposure and thyroid hormone status among raccoons inhabiting a perchlorate-contaminated site

Perchlorate is a water soluble anion that is readily accumulated in vegetation. It inhibits uptake of iodide into thyroid gland tissue, thereby reducing production of thyroid hormones. Potential raccoon food items including berries, fish, and vegetation collected at a contaminated site contained quantifiable concentrations of perchlorate as determined by ion chromatography. Therefore, we monitored resident raccoons for exposure to perchlorate by examining plasma perchlorate and thyroid hormone concentrations. Resulting analytical data failed to demonstrate perchlorate exposure among raccoons that likely consumed food items collected along perchlorate-contaminated water bodies. There were no correlations between triiodothyronine or thyroxine and thyroid stimulating hormone concentrations, but triiodothyronine concentrations in raccoon plasma were significantly higher in 2000 than in 2001 (p = 0.0081). These data suggest that natural attenuation and remedial efforts initiated in January of 2001 may have reduced perchlorate exposure among raccoons inhabiting this site from 2000 to 2001. Temporal, spatial, and analytical factors limited our ability to quantify exposure among raccoons, however, our data do not indicate that raccoons currently inhabiting this site are at risk for significant exposure to perchlorate and subsequent effects.     

Determination of ethanolamine,ethylene glycol and triethylene glycol by ion chromatography for laboratory and field biodegradation studies

The determination of alkanolamines and glycols in groundwater and subsurface environments is essential for environmental assessment, remediation and monitoring for selected industrial sites. Monoethanolamine (MEA), ammonium, sodium, magnesium and calcium detection was performed using cation exchange chromatography (IC) with suppressed conductivity detection. Acetate, chloride, nitrite, nitrate, phosphate, sulfate and oxalate were monitored employing anion exchange chromatography with suppressed conductivity. Detection of ethylene glycol (MEG) and triethylene glycol (TEG) and ethanol was carried out using ion exclusion chromatography with pulsed amperometric detection. Effective determination of MEA, MEG and TEG in complex groundwater matrices without compound transformation offered improved monitoring capabilities. This study presents robust analytical tools for MEA, MEG and TEG determination in biodegradation studies. Using ion chromatography offered significant advantages for the analyses of groundwater samples and laboratory bioreactor monitoring.     

超声提取-离子色谱法测定常见土壤中的高氯酸盐

建立了测定土壤中高氯酸盐的离子色谱法,通过前处理条件优化和色谱条件优化形成准确高效的测定方法,并采集实际土壤样品进行实验验证。称取 1.00 g土壤样品,用20 mL超纯水混合均匀,超声提取40 min,离心后采用水系微孔滤膜过滤的前处理方式,土壤中高氯酸盐的加标回收率最稳定;在淋洗液浓度和流速都满足测定条件的前提下,为了缩短高氯酸盐的保留时间,避免复杂基质干扰,延长淋洗液发生器的使用寿命以及保护色谱柱,选择淋洗液浓度为40 mmol/L,流速为1.0 mL/min。在优化条件下,高氯酸盐的方法检出限为0.04 mg/kg。实际样品加标中高氯酸盐的相对标准偏差为1.9%~8.8%,加标回收率为91.0%~106%,结果表明离子色谱法测定土壤中高氯酸盐简单、灵敏、快速。     

铵离子对COD测定的干扰及干扰的消除方法

水样中只存在铵离子时对COD的测定几乎没有影响,而当铵离子与氯离子同时存在时,除了氯离子带来的干扰外,铵离子也会对COD的测定产生干扰。针对此现象,研究建立了加碱氮吹法,此法可有效去除COD测定中浓度小于1 000 mg/L铵离子的干扰,并确定了最佳除铵离子条件为过量加碱、600 m L/min的氮气流量和3 h的通气时间。通过7次平行测定含铵离子干扰物的水样,该方法的相对标准偏差为3.3%~6.5%,加标回收率为90.2%~97.0%,表明方法具有较好的精密度和准确度,能够较准确测定含有铵离子干扰水样的COD。     

Changes in precipitation chemistry in Lithuania for 1981-2004

This paper considers the spatial and temporal variability in concentrations of the potentially acidifying ions in precipitation in Lithuania during the 1981-2004 period. Chemical analysis of precipitation included measurements of pH, conductivity, sulfate (SO4(2-)), nitrate (NO3-), chloride (Cl-), ammonium (NH4+), sodium (Na+), potassium (K+), and calcium (Ca2+). Temporal trends in the potentially acidifying ion concentrations in precipitation and wet deposition were evaluated using the non-parametric Mann-Kendall test and Sen's slope estimator. A statistically significant decline was observed in non-sea salt sulfate (nssSO4(2-)) and hydrogen (H+) ions concentrations (82% and 79%, respectively) and wet depositions (88% and 74%, respectively). Temporal trends both in concentration and wet deposition of nitrate and ammonium were not as pronounced as trends in sulfate concentration. Analysis of air mass backward trajectories was applied to reveal the influence of air mass originating in different regions on wet deposition of acidifying species in Lithuania. Sector analysis clearly showed that wet deposition of sulfur and nitrogen in Lithuania is to a large extent anthropogenic and the main source regions of acidifying species contributing to wet deposition in Lithuania are in South and Central Europe.     

Experimental investigation of cesium mobility in the course of secondary mineral formations in Hanford sediment columns at 50°C

Formation of secondary minerals and Cs mobility in Hanford sediments were investigated under conditions similar to the Hanford tank leak in a dynamic flow system at 50°C. The objectives were to (1) examine the nature and locations of secondary mineral phases precipitated in the sediments and (2) quantify the amount of Cs retained by the sediment matrix at 50°C. To this end, Hanford sediments were packed into 10-cm long columns and leached with simulated tank waste consisting of 1.4 M NaOH, 0.125 M NaAlO₂, 3.7 M NaNO₃, and 1.3 × 10^???4 M Cs at 50°C. Compositions of outflow solution were monitored with time for up to 25 days, and the columns were then segmented into four 2.5-cm long layers. The colloidal fraction in these segments was characterized in terms of mineralogy, particle morphology, Cs content, and short-range Al and Si structure. It was observed that cancrinite and sodalite precipitated at 50°C. Approximately 53% Cs was retained in the column treated by the simulated tank waste at this temperature. Cesium retention in the column was lowered in the high ionic strength solution due to competition from Na for the exchange sites. This can be explained by alteration of distribution and number of sorption sites which reduces the selectivity of Cs for Na, and through the formation of cancrinite and sodalite. The formation of hydroxide complexes in highly alkaline solutions could also contribute to relatively poor retention of Cs by hindering ion exchange mechanism.     

Biodegradation testing of radioactive waste forms

Biodegradation tests were conducted on solidified waste forms containing ion exchange resins contaminated with high levels of radioactive nuclides. These tests were part of a program to test waste forms in accordance with the U.S. NRC Branch Technical Position on Waste Forms. Small waste forms were manufactured using two different solidification agents, Portland Type I–II cement and vinyl ester-styrene (VES). Ion exchange material was taken from a filter system which had been used to remove radionuclides from highly contaminated water. As specified by NRC, the waste forms were evaluated for their resistance to biological degradation using the G21 and G22 procedures of the American Society for Testing Materials (ASTM). Results showed that microbial growth can be supported by the VES waste forms. The particular organisms used in the tests did not grow in the presence of the cement waste forms. It is also shown that the ASTM tests specified in the Technical Position are not suitable for the use intended. A different testing methodology is recommended which would provide direct verification of waste form integrity.Work supported by the U.S. Nuclear Regulatory Commission, Office of Nuclear Regulatory Research, under DOE Contract No. DE-AC07-761D01570.This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, or any of their employees, makes any warranty, expressed or implied, or assumes any legal liability or responsibility for any third party's use, or the results of such use, of any information, apparatus, product or process disclosed in this report, or represents that its use by such third party would not infringe privately owned rights. The views expressed in this report are not necessarily those of the U.S. Nuclear Regulatory Commission.     

Bioremediation of heavy metals using biostimulation in laboratory bioreactor

The present research study investigates bioremediation potential of biostimulated microbial culture isolated from heavy metals waste disposal contaminated site located at Bhayander (east), Mumbai, India. The physicochemical and microbial characterization including heavy metal contaminants have been studied at waste disposal site. The microorganisms adapted at heavy metal-contaminated environment were isolated, cultured, and biostimulated in minimal salt medium under aerobic conditions in a designed and developed laboratory bioreactor. Heavy metals such as Fe, Cu, and Cd at a selected concentration of 25, 50, and 100?μg/ml were taken in bioreactor wherein biostimulated microbial culture was added for bioremediation of heavy metals under aerobic conditions. The remediation of heavy metals was studied at an interval of 24?h for a period of 21?days. The biostimulated microbial consortium has been found effective for remediation of Cd, Cu, and Fe at higher concentration, i.e., 100?mg/l up to 98.5%, 99.6%, and 100%, respectively. Fe being a micronutrient was remediated completely compared to Cu and Cd. During the bioaccumulation of heavy metals by microorganisms, environmental parameters such as pH, total alkalinity, electronic conductivity, biological oxygen demand, chemical oxygen demand, etc. were monitored and assessed. The pilot scale study would be applicable to remediate heavy metals from waste disposal contaminated site to clean up the environment.     

A survey on the temporal and spatial distribution of perchlorate in the Potomac River

Samples of river water and treated drinking water were obtained from eight sites along the Potomac River between western Maryland and Washington DC. Samples were collected each month from October 2007 to September 2008 and analyzed for perchlorate by ion chromatography/mass spectrometry. Data on anions were also collected for seven of the twelve months. Data were analyzed to identify spatial and temporal patterns for the occurrence of perchlorate in the Potomac. Over the year of sampling, the largest monthly increase occurred from June to July, with levels then decreasing from July to September. Samples from the period between December and May had lower perchlorate concentrations, relative to the remainder of the study year. Spatially, higher levels of perchlorate were found at sites located in west-central Maryland, the eastern panhandle of West Virginia, and central northern Virginia, with levels decreasing slightly as the Potomac approaches Washington DC. Within the sampling boundaries, river (untreated) water perchlorate concentrations ranged from 0.03 μg L(-1) to 7.63 μg L(-1), averaged 0.67 ± 0.97 μg L(-1) over the year-long period and had a median value of 0.37 μg L(-1). There was no evidence that any of the existing drinking water treatment technologies at the sampling sites were effective in removing perchlorate. There were no correlations found between the presence of perchlorate and any of the anions or water quality parameters examined in the source water with the exception of a weak positive correlation with water temperature. Results from the summer (June-August) and fall (September-November) months sampled in this study were generally higher than from the winter and spring months (December-May). All but one of the locations had annual average perchlorate levels below 1 μg L(-1); however, 7 of the 8 sites sampled had river water perchlorate detections over 1 μg L(-1) and 5 of the 8 sites had treated water detections over this level.     

Particulate matter characterization at a coastal site in south-eastern Italy

Several samples of airborne particulate matter (PM), collected from 6th November to 6th December 2003 at a coastal site in the south-east of Italy, have been analyzed by different techniques to characterize elemental composition and morphological properties of the inorganic PM fraction and obtain preliminary results on anthropogenic contributions. Al, Cr, Cu, Fe, Mn, V, Pb, Ti, Ca and Zn mass concentrations, evaluated by an inductively coupled plasma atomic emission spectrometer, account for up to l% of the bulk PM mass in the investigated samples. According to geochemical calculations, Ca, Al, Fe and Mn are predominantly of crustal origin, while Cr, Cu, Pb, V, Ti and Zn heavy metals are of anthropogenic origin. Ion chromatography analyses have identified sulfate (SO(4)(2-)) nitrate (NO(3)(-)), sodium (Na(+)), and ammonium (NH(4)(+)) as the main ionic components accounting for up to 38% of the total PM mass and up to 90% of the total ionic mass. Besides ion chromatography, X-ray energy dispersive (EDX) microanalyses have revealed the high variability of Cl: its weight concentration varies from about 24% to below the detection limit (>or=0.5%) in the investigated samples. The marked anti-correlation between the excess of S and the Cl/Na ratio has allowed inferring that reactions between sea salt particles and acidic sulfates, which liberate HCl gas to the atmosphere leaving particles enriched in non-sea-salt sulfates, have significantly contributed to chloride depletion. Morphological analyses by scanning electron microscopy have shown that about 90% of the total sampled particles have a diameter 相似文献   

Solid waste characteristics and their relationship to gas production in tropical landfill

Solid waste characteristics and landfill gas emission rate in tropical landfill was investigated in this study. The experiment was conducted at a pilot landfill cell in Thailand where fresh and two-year-old wastes in the cell were characterized at various depths of 1.5, 3, 4.5 and 6 m. Incoming solid wastes to the landfill were mainly composed of plastic and foam (24.05%). Other major components were food wastes (16.8%) and paper (13.3%). The determination of material components in disposed wastes has shown that the major identifiable components in the wastes were plastic and foam which are resistant to biodegradation. The density of solid waste increased along the depth of the landfill from 240 kg m⁻³ at the top to 1,260 kg m⁻³ at the bottom. Reduction of volatile solids content in waste samples along the depth of landfill suggests that biodegradation of solid waste has taken place to a greater extent at the bottom of the landfill. Gas production rates obtained from anaerobic batch experiment were in agreement with field measurements showing that the rates increased along the depth of the landfill cell. They were found in range between 0.05 and 0.89 l kg⁻¹ volatile solids day⁻¹. Average emission rate of methane through the final cover soil layer was estimated as 23.95 g⁻²day⁻¹ and 1.17 g⁻²day⁻¹ during the dry and rainy seasons, respectively.     

Trace level determination of perchlorate in water matrices and human urine using ESI-FAIMS-MS

High-field asymmetric waveform ion mobility spectrometry (FAIMS) separates perchlorate from interfering isobaric ions of bisulfate and dihydrogenphosphate in the gas-phase. The use of a new FAIMS prototype and waveform generator, along with the use of a mixed carrier gas, in this electrospray ionisation (ESI)-FAIMS-mass spectrometry (MS) study gave a detection limit for perchlorate in a relatively "clean" matrix of tap water of 0.050 ppb. Flow injection analysis (FIA) of dilutions of fortified waste water, a fortified river water certified reference material (CRM; SLRS-4, National Research Council of Canada), and a fortified human urine Standard Reference Material (SRM; 2381, National Institute of Standards and Technology) gave detection limits of 0.37 ppb, 0.50 ppb, and 4.8 ppb, respectively, in the undiluted matrices.     

Performance of poly(vinyl alcohol) gel columns on the ion chromatographic determination of perchlorate in fertilizers

Interest in possible sources of perchlorate (ClO4) that could lead to environmental release has been heightened since the Environmental Protection Agency placed this anion on its Contaminant Candidate List for drinking water. Although recent investigations have suggested that fertilizers are minor contributors to environmental perchlorate contamination overall, there is still interest in screening commercial products for possible contamination and quantitating perchlorate when it is found. Ion chromatography (IC) has been used for this application owing to its speed, low detection limits, widespread availability, and moderate ruggedness relative to other techniques. However, fertilizer matrixes complicate the IC analysis relative to potable water matrixes. In this study, the performance of poly(vinyl alcohol) gel resin IC columns (100 mm and 150 mm) was evaluated for fertilizer matrixes using method EPA/600/R-01/026. The NaOH eluent included an organic salt, sodium 4-cyanophenoxide. Detection was by suppressed conductivity. A set of 55 different field samples representing 48 products and previously used by the EPA to assess occurrence of perchlorate in fertilizers (EPA/600/R-01/049) was reanalyzed on the 150 mm column. The 100 mm column was used to further investigate the positive hits. Both columns gave satisfactory performance in fertilizer matrixes, with spike recoveries (+/- 15%), assured reporting levels (0.5-225 microg g(-1) except for one at 1,000 microg g(-1)), accuracy (relative error < 30% always and most < 15%), and precision [injection-to-injection reproducibility < 3% relative standard deviation (RSD)] comparable to those reported in other studies. Performance did not vary substantially between column lengths. Lastly, the results of this investigation provided further evidence in support of the conclusions that had been reached previously by the EPA on the occurrence of perchlorate in fertilizers.     

Artemia salina as test organism for assessment of acute toxicity of leachate water from landfills

Artemia salina has, for the first time, been used as test organism for acute toxicity of leachate water from three landfills (the municipal landfills at Kristianstad, Sweden and Siauliai, Lithuania, and an industrial landfill at Stena fragmenting AB, Halmstad, as well as for leachate from Kristianstad treated in different ways in a pilot plan). Artemia can tolerate the high concentrations of chloride ions found in such waters. Large differences in toxicities were found, the leachate from Siauliai being the most toxic one. To increase the selectivity in the measurements, a fractionation was done by using ion exchange to separate ammonium/ammonia and metal ions from the leachate, and activated carbon adsorbents for organic pollutants. The influence of some metals and phenol compounds on the toxicity was investigated separately. It was found that most of the toxicity emanated from the ammonium/ammonia components in the leachate. However, there was also a significant contribution from organic pollutants, other than phenol compounds, since separate experiments had in this latter case indicated negligible impact. The concentrations of metals were at a level, shown by separate experiments, where only small contribution to the toxicity could be expected.     

Occurrence and exposure assessment of perchlorate, iodide and nitrate ions from dairy milk and water in Japan and Sri Lanka

Perchlorate is known to competitively interfere with iodide uptake by the thyroid gland and thereby human exposure to perchlorate is a public health concern. Prevalence of perchlorate in dairy milk is documented; nevertheless, co-occurrence of perchlorate with other thyroid-binding monovalent ions such as iodide and nitrate is not well understood. In this study, we analyzed perchlorate, iodide, and nitrate-N in dairy milk, water and other dairy-related samples collected from Japan and Sri Lanka. Concentrations of perchlorate in Japanese dairy milk samples ranged from 1.03 to 14.1 ng ml(-1); the corresponding concentrations in dairy milk and powdered milk from Sri Lanka were 1.14-38.5 ng ml(-1). Perchlorate concentrations in commercial milk were significantly higher in Japan than in Sri Lanka, while iodide and nitrate levels in milk between the two countries were comparable. All three ions were ubiquitously found in water samples from Japan and Sri Lanka. Analysis of colostrum and raw milk collected from cows fed with the same feed for over 30 days showed no significant temporal variations in perchlorate, iodide and nitrate-N concentrations. A significant positive correlation was found between the concentrations of perchlorate and iodide in Japanese commercial milk. The concentrations of perchlorate and nitrate-N in water samples analyzed from both countries also showed a significant positive correlation. The exposure estimation revealed that dairy milk provides a greater source for perchlorate and iodide, while water predominantly contributes nitrate-N intake for all age groups in both counties. Infants and children demonstrated the highest estimated perchlorate, iodide and nitrate-N intake on a body weight basis in comparison to other age groups. Therefore, further studies of risk associated with perchlorate may need to reconsider co-existence of iodine and other iodide transport inhibitors in food.     

Reaction kinetics and validity of BOD test for domestic wastewater released in marine ecosystems

With urbanization of coastal cities, marine pollution is becoming a severe problem. The rates of biodegradation, decomposition, and ratification of pollutants get slowed down due to salinity. The higher temperatures prevalent in tropical regions significantly affect reaction rates. Multiple factors influence the rate of biodegradation, making the process complex. Hence, prediction and evaluation of the assimilative capacity of the marine environment due to wastewater discharges is becoming a difficult task. Biochemical oxygen demand (BOD) is a wet oxidation process, which follows first-order kinetics. The values of kinetic rate constants are expected to differ with varying salinities and temperatures. Research is carried out using glucose-glutamic acid and domestic wastewater to evaluate the impact of salinity on biodegradation of carbonaceous waste at 20°C and 27°C. The findings confirm the hypothesis of slow biodegradation of carbonaceous organic matter in marine waters. An inverse relationship between rate of biodegradation and salinity was observed. BOD exertion at 20°C (5?days) and 27°C (3?days) for the marine environment is comparable at selected salinities thereby confirming the validity of BOD test of shorter duration at elevated temperature.