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1.
Approximately 190 kg of 2 μm‐diameter zero‐valent iron (ZVI) particles were injected into a test zone in the top 2 m of an unconfined aquifer within a trichloroethene (TCE) source area. A shear‐thinning fluid was used to enhance ZVI delivery in the subsurface to a radial distance of up to 4 m from a single injection well. The ZVI particles were mixed in‐line with the injection water, shear‐thinning fluid, and a low concentration of surfactant. ZVI was observed at each of the seven monitoring wells within the targeted radius of influence during injection. Additionally, all wells within the targeted zone showed low TCE concentrations and primarily dechlorination products present 44 d after injection. These results suggest that ZVI can be directly injected into an aquifer with shear‐thinning fluids to induce dechlorination and extends the applicability of ZVI to situations where other emplacement methods may not be viable.  相似文献   

2.
ZVI‐Clay is an emerging remediation approach that combines zero‐valent iron (ZVI)‐mediated degradation and in situ stabilization of chlorinated solvents. Through use of in situ soil mixing to deliver reagents, reagent‐contaminant contact issues associated with natural subsurface heterogeneity are overcome. This article describes implementation, treatment performance, and reaction kinetics during the first year after application of the ZVI‐Clay remediation approach at Marine Corps Base Camp Lejeune, North Carolina. Primary contaminants included trichloroethylene, 1,1,2,2‐tetrachloroethane, and related natural degradation products. For the field application, 22,900 m3 of soils were treated to an average depth of 7.6 m with 2% ZVI and 3% sodium bentonite (dry weight basis). Performance monitoring included analysis of soil and water samples. After 1 year, total concentrations of chlorinated volatile organic compounds (CVOCs) in soil samples were decreased by site‐wide average and median values of 97% and >99%, respectively. Total CVOC concentrations in groundwater were reduced by average and median values of 81% and >99%, respectively. In several of the soil and groundwater monitoring locations, reductions in total CVOC concentrations of greater than 99.9% were apparent. Further reduction in concentrations of chlorinated solvents is expected with time. Pre‐ and post‐mixing average hydraulic conductivity values were 1.7 × 10?5 and 5.2 × 10?8 m/s, respectively, indicating a reduction of about 2.5 orders of magnitude. By achieving simultaneous contaminant mass depletion and hydraulic conductivity reduction, contaminant flux reductions of several orders of magnitude are predicted.  相似文献   

3.
Toxic and carcinogenic effects of arsenic in drinking water continue to impact people throughout the world and arsenic remains common in groundwater at cleanup sites and in areas with natural sources. Advances in groundwater remediation are needed to attain the low concentrations that are protective of human health and the environment. In this article, we present the successful use of a permeable reactive barrier (PRB) utilizing sulfate reduction coupled with zero‐valent iron (ZVI) to remediate the leading edge of a dissolved arsenic plume in a wetland area near Tacoma, Washington. A commercially available product (EHC‐M®, Adventus Americas Inc., Freeport, Illinois) that contains ZVI, organic carbon substrate, and sulfate was injected into a reducing, low‐seepage‐velocity aquifer elevated in dissolved arsenic and iron from a nearby, slag‐containing landfill. Removal effectiveness was strongly correlated with sulfate concentration, and was coincident with temporary redox potential (Eh) reductions, consistent with arsenic removal by iron sulfide precipitation. The PRB demonstrates that induced sulfate reduction and ZVI are capable of attaining a regulatory limit of 5 µg/L total arsenic, capturing of 97% of the arsenic entering the PRB, and sustaining decreased arsenic concentrations for approximately 2 years, suggesting that the technology is appropriate for consideration at other sites with similar hydrogeochemical conditions. The results indicate the importance of delivery and longevity of minimum sulfate concentrations and of maintaining sufficient dissolved organic carbon and/or microscale ZVI to precipitate FeS, a precursor phase to arsenic‐bearing pyrite that may provide a stable, long‐term sink for arsenic.  相似文献   

4.
Successful in situ groundwater remediation relies on the adequate distribution of treatment materials within the subsurface. Zero‐valent iron (ZVI) is widely used for the remediation of soils contaminated with chlorinated organic compounds. Because ZVI is a solid, various techniques are used to distribute ZVI in the subsurface; however, a major uncertainty in this process involves determining the distribution of the iron during emplacement. A method of mapping the distribution of ferromagnetic material such as ZVI is by magnetic susceptibility (MS), a novel approach that is highly sensitive, quantitative, objective, and easily applied in field. The method has been tested in the laboratory on synthetic cores containing EHC®, an organic amendment containing 40 to 50% ZVI, using an MS meter with two types of sensors (loop and handheld). Both sensors have high sensitivity (e.g., 1% disseminated EHC is easily detected), whereas the hand‐held sensor has greater spatial resolution (e.g., differences are notable on a scale of 1 cm). Following the laboratory studies, the handheld instrument was used to perform field measurements for multiple pilot studies and a full‐scale application of EHC using various delivery methods (pneumatic fracturing, hydraulic fracturing, and direct injection) to construct a biobarrier at a field remedial site. The MS method has proven invaluable in quantifying amendment distribution and ensuring appropriate application of this remedial technology.  相似文献   

5.
A method is presented to evaluate ground water residence time in a zero‐valent iron (ZVI) permeable reactive barrier (PRB) using radon‐222 (222Rn) as a radioactive tracer. Residence time is a useful indicator of PRB hydraulic performance, with application to estimating the volumetric rate of ground water flow through a PRB, identifying flow heterogeneity, and characterizing flow conditions over time as a PRB matures. The tracer method relies on monitoring the decay of naturally occurring aqueous 222Rn as ground water flows through a PRB. Application of the method at a PRB site near Monticello, Utah, shows that after 8 years of operation, residence times in the ZVI range from 80 to 486 h and correlate well with chemical parameters (pH, Ca, SO4, and Fe) that indicate the relative residence time. Residence times in this case study are determined directly from the first‐order decay equation because we show no significant emanation of 222Rn within the PRB and no measurable loss of 222Rn other than by radioactive decay.  相似文献   

6.
Recently, increased industrial and agriculture activities have resulted in toxic metal ions, which has increased public concern about the quality of surface and groundwater. Various types of physical, biological, and chemical approaches have been developed to remove surface and groundwater metal ions contaminants. Among these practices, zero‐valent iron (ZVI) is the most studied reactive material for environmental clean‐up over the last two decade and so. Although ZVI can remove the contaminants even more efficiently than any other reactive materials. However, low reactivity due to its intrinsic passive layer, narrow working pH, and the loss of hydraulic conductivity due to the precipitation of metal hydroxides and metal carbonates limits its wide‐scale application. The aim of this work is to document properties, synthesis, and reaction mechanism of ZVI for the treatment of metal ions from the surface and groundwater in recent 10 years (2008–2018). So far, different modified techniques such as conjugation with support, bimetal alloying, weak magnetic field, and ZVI/oxidant coupling system have been developed to facilitate the use of ZVI in various environmental remediation scenarios. However, some challenges still remain to be addressed. Therefore, development and research in this field are needed to overcome or mitigate these limitations.  相似文献   

7.
A pilot‐scale zero valent iron (ZVI) Permeable Reactive Barrier (PRB) was installed using an azimuth‐controlled ‐vertical hydrofracturing at an industrial facility to treat a chlorinated Volatile Organic Compound (VOC) plume. Following ZVI injection, no significant reduction in concentration was observed to occur with the exception of some multilevel monitoring wells, which also showed high levels of total organic carbon (TOC). These patterns suggested that the zero valent iron was not well distributed in the PRB creating leaky conditions. The geochemical data indicated reducing conditions in these areas where VOC reduction was observed, suggesting that biotic processes, associated to the guar used in the injection of the iron, could be a major mechanism of VOC degradation. Compound‐Specific Isotope Analysis (CSIA) using both carbon and chlorine stable isotopes were used as a complementary tool for evaluating the contribution of abiotic and biotic processes to VOC trends in the vicinity of the PRB. The isotopic data showed enriched isotope values around the PRB compared to the isotope composition of the VOC source confirming that VOC degradation is occurring along the PRB. A batch experiment using site groundwater collected near the VOC source and the ZVI used in the PRB was performed to evaluate the site‐specific abiotic isotopic fractionation patterns. Field isotopic trends, typical of biodegradations were observed at the site and were different from those obtained during the batch abiotic experiment. These differences in isotopic trends combined with changes in VOC concentrations and redox parameters suggested that biotic processes are the predominant pathways involved in the degradation of VOCs in the vicinity of the PRB.  相似文献   

8.
Agricultural subsurface drainage waters containing nutrients (nitrate/phosphate) and pesticides are discharged into neighboring streams and lakes, frequently producing adverse environmental impacts on local, regional, and national scales. On‐site drainage water filter treatment systems can potentially prevent the release of agricultural contaminants into adjacent waterways. Zero valent iron (ZVI) and sulfur‐modified iron (SMI) are two types of promising filter materials that could be used within these treatment systems. Therefore, water treatment capabilities of three ZVI and three SMI filter materials were evaluated in the laboratory. Laboratory evaluation included saturated falling‐head hydraulic conductivity tests, contaminant removal batch tests, and saturated solute transport column experiments. The three ZVI and the three SMI filter materials, on average, all had a sufficient hydraulic conductivity greater than 1 × 10–3 cm/s. Batch test results showed a phosphate decrease of at least 94% for all tests conducted with the ZVI and SMI. Furthermore, the three SMI filter materials removed at least 86% of the batch test nitrate originally present, while batch tests for one of the ZVI filter materials exhibited an 88% decrease in the pesticide, atrazine. Saturated solute transport column experiments were carried on the best ZVI filter material, or the best SMI filter material, or both together, in order to better evaluate drainage water treatment effectiveness and efficiency. Results from these column tests additionally document the drainage water treatment ability of both ZVI and SMI to remove the phosphate, the ability of SMI to remove nitrate, and the ability of a select ZVI material to remove atrazine. Consequently, these findings support further investigation of ZVI and SMI subsurface drainage water treatment capabilities, particularly in regard to small‐ and large‐scale field tests.  相似文献   

9.
The removal of chemical oxygen demand (COD) and phenol from olive oil mill wastewaters (OOMW) was investigated experimentally by using conventional Fenton (CFP) and Fenton type processes (FTP) with zero valent iron (ZVI). Different operational parameters such as initial pH, Fe2+, Fe0, and H2O2 concentrations were examined. Kinetic studies in terms of COD and phenol removals for both CFP and FTP were performed. The original pH value (4.6) of OOMW for CFP was found as the optimum pH. The determined optimum conditions are [Fe2+] = 1500 mg L?1, [H2O2] = 1750 mg L?1, and pH = 4.6 for CFP; [Fe0] = 2000 mg L?1, [H2O2] = 2000 mg L?1, and pH = 3 for FTP. 82.4% COD and 62% phenol removals were performed under the optimum conditions by CFP, while 82% COD and 63.4% phenol were removed by FTP. According to the results of kinetic studies, it was observed that COD and phenol were removed by FTP more rapidly, compared to CFP. Consequently, it was determined that both CFP and FTP were effective processes for the pretreatment of OOMW.  相似文献   

10.
MIN3P, a multicomponent reactive transport model for variably saturated porous media, is used to simulate the outputs of column tests carried out using zero valent iron (ZVI) for nickel contaminated groundwater remediation. The objective of this study is to investigate the main chemical reactions involved in contaminant removal and the main causes of the reactivity decline of ZVI over time. According to the results of the model the major causes of ZVI reactivity loss is identified in the mineral precipitation of α‐FeOOH on iron surface that probably caused ZVI passivation and led to a decline of the electron transfer rate. An existing empirical relationship between mineral precipitation and the reactivity loss of ZVI, included in the model, reproduced the changes in nickel removal observed during different laboratory column tests.  相似文献   

11.
There are many fundamental problems with the injection of nano‐zero‐valent iron (NZVI) particles to create permeable reactive barrier (PRB) treatment zone. Among them the loss of medium porosity or pore blocking over time can be considered which leads to reduction of permeability and bypass of the flow and contaminant plume up‐gradient of the PRB. Present study provides a solution for such problems by confining the target zone for injection to the gate in a funnel‐and‐gate configuration. A laboratory‐scale experimental setup is used in this work. In the designed PRB gate, no additional material from porous media exists. NZVI (d50 = 52 ± 5 nm) particles are synthesized in water mixed with ethanol solvent system. A steady‐state condition is considered for the design of PRB size based on the concept of required contact time to obtain optimum width of PRB gate. Batch experiment is carried out and the results are used in the design of PRB gate width (~50 mm). Effect of high initial NO3‐N concentration, NZVI concentration, and pore velocity of water in the range of laminar groundwater flow through porous media are evaluated on nitrate‐N reduction in PRB system. Results of PRB indicate that increasing the initial NO3‐N concentration and pore velocity has inhibitor effect—against the effect of NZVI concentration—on the process of NO3‐N removal. Settlement velocity (S.V.) of injected NZVI with different concentrations in the PRB is also investigated. Results indicate that the proposed PRB can solve the low permeability of medium in down‐gradient but increasing of the S.V. especially at higher concentration is one of the problems with this system that needs further investigations.  相似文献   

12.
Remediation of groundwater contaminated by chlorinated hydrocarbons via in situ technologies such as direct injection of nanoscale zero valent iron (ZVI, Fe(O)) particles is increasingly common. However, assessing target compound degradation by abiotic processes is difficult because (1) the injection may displace the contaminant plume so that concentration measurements alone are often inconclusive and (2) biodegradation may also occur, making it challenging to identify and evaluate the abiotic degradation component. In this study, trichloroethylene (TCE) and 1,1,1-trichloroethane (1,1,1-TCA) were treated in a highly heterogeneous hydrogeologic setting. The purpose of this study was to evaluate the potential for compound-specific stable isotope analysis (CSIA) to monitor the effectiveness of ZVI injection by assessing TCE and 1,1,1-TCA degradation. Prior to ZVI injection, carbon isotope measurements demonstrated biodegradation of TCE by native microorganisms. This in situ biodegradation was quantified by measuring the enrichment of 13C in TCE samples downstream of the suspected source. When ZVI was injected through only two injection wells, no changes in TCE and 1,1,1-TCA isotope signatures were detected compared to preinjection values. In contrast, when ZVI was injected through 11 wells covering a greater portion of the contaminated area, 5 out of 10 monitoring wells showed further enrichment of 13C in either TCE or 1,1,1-TCA, indicating additional target compound transformation. The abiotic nature of this TCE transformation was confirmed through temporal trends in carbon isotope values of the putative transformation products cis-dichloroethylene (cis-DCE), ethene and ethane. This demonstrates the usefulness of CSIA in distinguishing abiotic vs. biotic transformation in the field.  相似文献   

13.
Toxic effects of five commonly used pesticides on the biomass of a municipal activated sludge system were determined on the basis of the reduction in the oxygen uptake rate (OUR) and specific oxygen uptake rate (SOUR). Toxicity levels of the selected pesticides were determined by employing a modified OECD 209 (Organisation for Economic Cooperation and Development) method which was performed as batch experiments using a respirometer. Copper sulphate (CuSO4 · 5 H2O), copper oxychloride (Cu2Cl(OH)3), copper calcium oxychloride (CaCu3Cl2(OH)6) as copper‐based pesticides and chlorsulphuron (C12H12ClN5O4S), 2,4‐dichlorophenoxyacetic acid (2,4‐D) (C8H6Cl2O3) as synthetic organic pesticides were selected for the experiments. The EC50 values were determined to be 78, 249 and 281 mg/L for CuSO4 · 5 H2O, Cu2Cl(OH)3 and CaCu3Cl2(OH)6, respectively. Corresponding values for C12H12ClN5O4S and 2,4‐D were 860 and 3664 mg/L, respectively. Results indicated that toxicity effects of copper‐based pesticides were higher than that of synthetic organic pesticides. CuSO4 · 5 H2O was found to exert the highest toxicity among the copper‐based pesticides, whereas, C12H12ClN5O4S was determined to be the most toxic among the organic pesticides on activated sludge biomass.  相似文献   

14.
Lepidocrocite (γ‐FeOOH) nanoparticles were synthesized from iron(II) sulfate solution and characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform‐IR (FT‐IR), nitrogen adsorption, and point of zero charge pH (pHPZC) analyses. TEM, XRD, and FT‐IR analyses proved the synthesis of nano‐lepidocrocite. Surface area and pHPZC of the synthesized lepidocrocite were 68.1 m2 g?1 and 4.8, respectively. Utilization of the synthesized lepidocrocite in the adsorption of Lanacron brown S‐GL (LBS‐GL) from aqueous solutions was investigated, and the effect of lepidocrocite dosage, pH, temperature, and contact time on this process were optimized and modeled using response surface methodology approach. The lepidocrocite dosage of 0.015 g, pH 3.5, temperature of 38°C, and contact time of 100 min were determined as optimum adsorption conditions. Isotherm and kinetics of the adsorption process were analyzed at the optimum conditions. The equilibrium data were fitted well to the Langmuir isotherm model. The maximum monolayer adsorption capacity was 528.21 mg g?1. The adsorption process was described by the pseudo‐second‐order kinetic model. Furthermore, the effect of pH on the desorption of LBS‐GL was investigated. High LBS‐GL desorption efficiency was achieved at a high pH value.  相似文献   

15.
The decomposition of dichloroacetic acid (DCAA) in water using a UV/H2O2/micro‐aeration process was investigated in this paper. DCAA cannot be removed by UV radiation, H2O2 oxidation or micro‐aeration alone, while UV/H2O2/micro‐aeration combination processes have proved effective and can degrade this compound completely. With initial concentrations of about 110 μg/L, more than 95.1% of DCAA can be removed in 180 min under UV intensity of 1048.7 μW/cm2, H2O2 dosage of 30 mg/L and micro‐aeration flow rate of 2 L/min. However, more than 30 μg/L of DCAA was left after 180 min by UV/H2O2 combination process without micro‐aeration with the same UV intensity and H2O2 dosage. The effects of applied UV radiation intensity, H2O2 dose, initial DCAA concentration and pH on the degradation of DCAA have been examined in this study. Degradation mechanisms of DCAA with hydroxyl radical oxidation have been discussed. The removal rate of DCAA was sensitive to operational parameters. There was a linear relationship between rate constant k and UV intensity and initial H2O2 concentration, which indicated that a higher removal capacity can be achieved by improvement of both factors. A newly found nitrogenous disinfection by‐product (N‐DBP)‐DCAcAm, which has the potential to form DCAA, was easier to remove than DCAA by UV/H2O2 and UV/H2O2/micro‐aeration processes. Finally, a preliminary cost comparison revealed that the UV/H2O2/micro‐aeration process was more cost‐effective than the UV/H2O2 process in the removal of DCAA from drinking water.  相似文献   

16.
The present work focuses on the performance of Fenton, sono‐Fenton, and sono‐photo‐Fenton processes for the oxidation of phenol present in aqueous solution. The effects of H2O2 concentration, Fe2+ concentration, pH, and initial phenol concentration on the oxidation of phenol were studied. The optimum Fe2+ and H2O2 concentrations for the Fenton process were 45 and 800 mg/L, respectively. For the sono‐Fenton process, the optimum Fe2+ and H2O2 concentrations were 30 and 800 mg/L, respectively. The optimal conditions for the sono‐photo‐Fenton process were found to be 20 mg/L of Fe2+ and 700 mg/L of H2O2. The optimum pH was found to be 3 for the processes investigated in the present study. The analysis of results showed that the sono‐photo‐Fenton method reduced the Fe2+ concentration by 30–50% and the H2O2 concentration by 12.5%. It was found that the sono‐photo‐Fenton technique showed better performance than the Fenton and sono‐Fenton processes for the oxidation of phenol. A lumped kinetic model was used to predict the chemical oxygen demand reduction and the model was found to fit the data.  相似文献   

17.
Fenton process was investigated for the purpose of biological sludge disintegration. The Box–Wilson experimental design was employed to evaluate the effects of major process variables (Fe(II) and H2O2 concentrations) on both disintegration and dewatering performance of sludge. Results showed that 4 g Fe(II)/kg total solids (TSs) and 60 g H2O2/kg TS are efficient for floc disintegration. Fenton pre‐treatment enhanced the biodegradability of sludge. For 4 g Fe(II)/kg TS and 60 g H2O2/kg TS, 19.4% higher methane production was achieved compared to raw sludge in biochemical methane potential assay. Fenton pre‐treatment resulted in the release of organic sludge components into the liquid phase. For 4 g Fe(II)/kg TS and 60 g H2O2/kg TS, dissolved organic carbon and total nitrogen in sludge's supernatant increased by 75.74 and 60.60%, respectively. Fenton pre‐treatment enhanced the filterability of sludge and it can be applied for conditioning purpose before mechanical dewatering units.  相似文献   

18.
The effect of extraordinary degradation of phenol organics on the SnO2‐Sb2O3/Ti electrode is investigated through experimental research and theoretical analysis. The phenol organics contained 4‐chloro‐phenol, 4‐bromo‐phenol, and 2‐iodo‐phenol. At a current density of 4 mA cm–2 and an electrolysis time of 12 h, the degradation efficiency of the phenols was over 98% with a relatively short degradation time, whereas the degradation time of the PbO2/Ti electrode surpassed 40 h while delivering 100% disposal efficiency. Therefore, the effectiveness of electrochemical (EC) oxidation by the SnO2‐Sb2O3/Ti was superior to that of the PbO2/Ti electrode. At the same time, the SnO2‐Sb2O3/Ti had higher oxygen generation potential and lower electron consumption than the other electrodes. This was mainly due to the effect of the middle Sb2O3 layer, which due to its high porosity and good catalytic effect, contributed to a better catalysis than the SnO2 part.  相似文献   

19.
Pharmaceutical compounds, widely produced and used all around the world, are partly responsible for the widespread water pollution in the environment. Carbamazepine (CBZ) is an antiepileptic drug that persists in the environment for many years. In the present study, we used the TiO2/UV, nanoparticulate zero‐valent iron (NZVI), and NZVI/H2O2 treatment processes to compare efficiency of CBZ removal from water. Influence of NZVI loading, H2O2 concentration, TiO2 loading, UV lamp power, and the matrix (distilled water and groundwater) on CBZ removal efficiency was evaluated using full factorial design. Results indicated that the NZVI/H2O2 process oxidized CBZ within 5 min. On the other hand, the NZVI process alone did not reduce CBZ concentration after 120 min of process time. The NZVI/H2O2 process was equally effective in CBZ removal from both distilled water and groundwater whereas the TiO2/UV process was less effective due to the presence of ions in groundwater. CBZ removal efficiency of the TiO2/UV process declined 30% when the matrix was changed from distilled water to groundwater. Negative divalent ions, i.e., and , were the main cause of reduction of CBZ removal efficiency from groundwater. It is likely that these two ions adsorb onto, and consequently prevent the superoxide anion and hydroxyl radical OH? from being generated on, the surface of the TiO2.  相似文献   

20.
Immediately before the extinction of the end‐Guadalupian (Middle Permian; ca 260 Ma), a significant change to the global carbon cycle occurred in the superocean Panthalassa, as indicated by a prominent positive δ13C excursion called the Kamura event. However, the causes of this event and its connection to the major extinction of marine invertebrates remain unclear. To understand the mutual relationships between these changes, we analyzed the sulfur isotope ratio of the carbonate‐associated sulfate (CAS) and HCl‐insoluble residue, as well as the carbon isotope ratio of bulk organic matter, for the Middle‐Upper Permian carbonates of an accreted mid‐oceanic paleo‐atoll complex from Japan, where the Kamura event was first documented. We detected the following unique aspects of the stable carbon and sulfur isotope records. First, the extremely high δ13C values of carbonate (δ13Ccarb) over +5 ‰ during the Capitanian (late Guadalupian) were associated with large isotopic differences between carbonate and organic matter (Δ13C = δ13Ccarb ? δ13Corg). We infer that the Capitanian Kamura event reflected an unusually large amount of dissolved organic matter in the expanded oxygen minimum zone at mid‐depth. Second, the δ34S values of CAS (δ34SCAS) were inversely correlated with the δ13Ccarb values during the Capitanian to early Wuchiapingian (early Late Permian) interval. The Capitanian trend may have appeared under increased oceanic sulfate conditions, which were accelerated by intense volcanic outgassing. Bacterial sulfate reduction with increased sulfate concentrations in seawater may have stimulated the production of pyrite that may have incorporated iron in pre‐existing iron hydroxide/oxide. This stimulated phosphorus release, which enhanced organic matter production and resulted in high δ13Ccarb. Low δ34SCAS values under high sulfate concentrations were maintained and the continuous supply of sulfate cannot by explained only by the volcanic eruption of the Emeishan Trap, which has been proposed as a cause of the extinction. The Wuchiapingian δ34SCAS–δ13Ccarb correlation, likely related to low sulfate concentration, may have been caused by the removal of oceanic sulfate through the massive evaporite deposition.  相似文献   

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