Comparison of volatile organic compounds in stormwater and groundwater in Seoul metropolitan city,South Korea

Volatile organic compounds (VOCs) detected in stormwater were compared with VOCs present in emission sources, air, groundwater, and influent to sewage treatment plants in Seoul to understand their fate and transport in the urban hydrological system. Stormwater is a carrier of non-point source pollutants and contains VOCs from land surfaces and air. Samples of stormwater and influent to sewage treatment plants were collected and analyzed for 61 VOCs, while the VOCs in emission sources, air and groundwater were investigated through literature reviews for comparison. The results showed that the most frequently detected VOCs in stormwater were similar to those in air. However, the atmospheric concentrations of benzene, toluene, ethylbenzene, and xylenes (BTEX), and methyl tertiary-butyl ether (MTBE) were too low to explain their frequent detection and high concentrations in stormwater. As a result, land surfaces seem to be a primary source of these VOCs in stormwater. Comparison of the VOCs in stormwater and groundwater showed that toluene and MTBE were frequently detected in both media, but more often and at higher concentrations in stormwater. This finding indicates that stormwater recharge is a source of toluene and MTBE in groundwater. Regarding groundwater, land surfaces seem to be a primary source of toluene, while urban air is the primary source in the case of MTBE. Specifically, the MTBE values in air were sufficiently high to explain its levels in groundwater, which had continually increased and remained low afterward. Furthermore, the high ratios of TEX (toluene, ethylbenzene, and xylenes) to benzene and MTBE in stormwater indicated that TEX had additional sources other than vehicles, most likely hydrocarbon solvents. These solvents seem to be a primary source of TEX and other frequently detected VOCs in stormwater. However, trichloroethylene (TCE), tetrachloroethylene (PCE) and their dechlorination intermediates were far more frequently detected and at higher concentrations in groundwater than in stormwater. Additionally, their concentrations frequently exceeded the water-quality criteria. It seems that halogenated solvents had produced contamination plumes of these chlorinated VOCs in the Seoul aquifer. Based on VOCs detected in Seoul, stormwater was mixed with groundwater in combined sewers and flowed into sewage treatment plants. The results imply that organic solvents should be handled with extreme care to protect groundwater quality.     

Tracing groundwater with low-level detections of halogenated VOCs in a fractured carbonate-rock aquifer,Leetown Science Center,West Virginia,USA

Measurements of low-level concentrations of halogenated volatile organic compounds (VOCs) and estimates of groundwater age interpreted from ³H/³He and SF₆ data have led to an improved understanding of groundwater flow, water sources, and transit times in a karstic, fractured, carbonate-rock aquifer at the Leetown Science Center (LSC), West Virginia. The sum of the concentrations of a set of 16 predominant halogenated VOCs (TDVOC) determined by gas chromatography with electron-capture detector (GC–ECD) exceeded that possible for air–water equilibrium in 34 of the 47 samples (median TDVOC of 24,800 pg kg⁻¹), indicating that nearly all the water sampled in the vicinity of the LSC has been affected by addition of halogenated VOCs from non-atmospheric source(s). Leakage from a landfill that was closed and sealed nearly 20 a prior to sampling was recognized and traced to areas east of the LSC using low-level detection of tetrachloroethene (PCE), methyl chloride (MeCl), methyl chloroform (MC), dichlorodifluoromethane (CFC-12), and cis-1,2-dichloroethene (cis-1,2-DCE). Chloroform (CHLF) was the predominant VOC in water from domestic wells surrounding the LSC, and was elevated in groundwater in and near the Fish Health Laboratory at the LSC, where a leak of chlorinated water occurred prior to 2006. The low-level concentrations of halogenated VOCs did not exceed human or aquatic-life health criteria, and were useful in providing an awareness of the intrinsic susceptibility of the fractured karstic groundwater system at the LSC to non-atmospheric anthropogenic inputs. The ³H/³He groundwater ages of spring discharge from the carbonate rocks showed transient behavior, with ages averaging about 2 a in 2004 following a wet climatic period (2003–2004), and ages in the range of 4–7 a in periods of more average precipitation (2008–2009). The SF₆ and CFC-12 data indicate older water (model ages of 10s of years or more) in the low-permeability shale of the Martinsburg Formation located to the west of the LSC. A two-a record of specific conductance, water temperature, and discharge recorded at 30-min intervals demonstrated an approximately 3-month lag in discharge at Gray Spring. The low groundwater ages of waters from the carbonate rocks support rapid advective transport of contaminants from the LSC vicinity, yet the nearly ubiquitous occurrence of low-level concentrations of halogenated VOCs at the LSC suggests the presence of long-term persistent sources, such as seepage from the closed and sealed landfill, infiltration of VOCs that may persist locally in the epikarst, exchange with low-permeability zones in fractured rock, and upward leakage of older water that may contain elevated concentrations of halogenated VOCs from earlier land use activities.     

Fate and transport of volatile organic compounds in glacial till and groundwater at an industrial site in Northern Ireland

Volatile organic compound (VOC) contamination of subsurface geological material and groundwater was discovered on the Nortel Monkstown industrial site, Belfast, Northern Ireland. The objectives of this study were to (1) investigate the characteristics of the geological material and its influences on contaminated groundwater flow across the site using borehole logs and hydrological evaluations, and (2) identify the contaminants and examine their distribution in the subsurface geological material and groundwater using chemical analysis. This report focuses on the eastern car park (ECP) which was a former storage area associated with trichloroethene (TCE) degreasing operations. This is where the greatest amount of volatile organic compounds (VOCs), particularly TCE, were detected. The study site is on a complex deposit of clayey glacial till with discontinuous coarser grained lenses, mainly silts, sands and gravel, which occur at 0.45–7.82 m below ground level (bgl). The lenses overall form an elongated formation that acts as a small unconfined shallow aquifer. There is a continuous low permeable stiff clayey till layer beneath the lenses that performs as an aquitard to the groundwater. Highest concentrations of VOCs, mainly TCE, in the geological material and groundwater are in these coarser lenses at ∼4.5–7 m bgl. Highest TCE measurements at 390,000 μg L⁻¹ for groundwater and at 39,000 μg kg⁻¹ at 5.7 m for geological material were in borehole GA19 in the coarse lens zone. It is assumed that TCE gained entrance to the subsurface near this borehole where the clayey till was thin to absent above coarse lenses which provided little retardation to the vertical migration of this dense non-aqueous phase liquid (DNAPL) into the groundwater. However, TCE is present in low concentrations in the geological material overlying the coarse lens zone. Additionally, VOCs appear to be associated with poorly drained layers and in peat <3.0 m bgl in the ECP. Some indication of natural attenuation as VOCs degradation products vinyl chloride (VC) and dichloromethane (DCM) also occur on the site.     

GIS-based colour composites and overlays to delineate heavy metal contamination zones in the shallow alluvial aquifers, Ankaleshwar industrial estate, south Gujarat, India

In an attempt to delineate heavy metal contamination precincts and to evaluate the extent and degree of toxic levels, besides their possible sources, 38 water samples from Ankaleshwar Industrial Estate, south Gujarat, India were analyzed. By clutching geochemical analyses and GIS-based colour composites areas depicting anomalously high concentration of heavy metals (Mo, Zn, Pb, Ni, Co, Cd, etc.) in the groundwater were revealed. The multicomponent overlays in grey-scale facilitated in identifying situates of heavy metal ‘hot spots’, and lateral protuberances of the contamination plume around defile stretch of the main stream Amla Khadi flowing through the area. The multiple pollution plumes emerging from other parts of the area further coincide with effluent laden streams and small channels indicating industrial establishments as major sources of groundwater contamination. Influent nature of the streams, accelerated infiltration process, high mass influx and shallow groundwater table are the factors conducive for easy access of heavy metals to the phreatic aquifers affecting over 20 km² area. On the basis of P/U ratios (concentration of metals in polluted water to unpolluted water), geogenic and anthropogenic sources have been identified. Very high levels of technogenic elements present in the ground water raise concerns about possible migration into food crops, as the area is an important horticultural locale and is highly cultivated.     

苯、甲苯对粒状铁去除四氯乙烯影响的柱实验研究

挥发性氯代烃和石油烃类污染是地下水中最常见的混合污染类型,而且这两类污染物毒性极强,对人类危害非常严重。文中选取具有代表性的四氯乙烯、苯和甲苯为研究对象,采用柱实验的方法研究苯和甲苯在粒状铁反应系统中吸附平衡后,对粒状铁去除四氯乙烯的机理及反应动力学的影响。在实验装置运行的过程中,苯、甲苯和四氯乙烯的浓度始终控制在2mg/L左右的水平。实验结果表明:苯或甲苯的存在对被还原的产物组成没有影响,主要氯代中间产物均为TCE、1,1-DCE、cis-1,2-DCE和VC,但组成比例略有不同。苯和甲苯的存在对去除速率有影响,即苯对四氯乙烯的去除有促进作用,去除速率平均提高13.5%;而甲苯则抑制四氯乙烯的去除,去除速率平均降低13.8%。对比控制柱,苯和甲苯存在时对出水水化学变化的影响没有明显差异。     

Hydrochemistry of urban groundwater in Seoul, South Korea: effects of land-use and pollutant recharge

The ionic and isotopic compositions (δD, δ¹⁸O, and ³H) of urban groundwaters have been monitored in Seoul to examine the water quality in relation to land-use. High tritium contents (6.1–12.0 TU) and the absence of spatial/seasonal change of O–H isotope data indicate that groundwaters are well mixed within aquifers with recently recharged waters of high contamination susceptibility. Statistical analyses show a spatial variation of major ions in relation to land-use type. The major ion concentrations tend to increase with anthropogenic contamination, due to the local pollutants recharge. The TDS concentration appears to be a useful contamination indicator, as it generally increases by the order of forested green zone (average 151 mg/l), agricultural area, residential area, traffic area, and industrialized area (average 585 mg/l). With the increased anthropogenic contamination, the groundwater chemistry changes from a Ca–HCO₃ type toward a Ca–Cl(+NO₃) type. The source and behavior of major ions are discussed and the hydrochemical backgrounds are proposed as the basis of a groundwater management plan.     

Contamination and potential mobility assessment of heavy metals in urban soils of Hangzhou,China: relationship with different land uses

Concentration and distribution of heavy metals (Cd, Cu, Pb and Zn) in urban soils of Hangzhou, China, were measured based on different land uses. The contamination degree of heavy metals was assessed on the basis of pollution index (PI), integrated pollution index (IPI) and geoaccumulation index (I _geo). The 0.1 mol l⁻¹ HCl extraction procedure and gastric juice simulation test (GJST) were used to evaluate the potential mobility and environmental risk of heavy metals in urban soils. The average concentration of Cd, Cu, Pb and Zn in urban soils was measured at 1.2 (with a range of 0.7–4.6), 52.0 (7.4–177.3), 88.2 (15.0–492.1) and 206.9 (19.3–1,249.2) mg kg⁻¹, respectively. The degree of contamination increased in the order of industrial area (IA) > roadside (RS) > residential and commercial areas (RC) > public park and green areas (PG). The PIs for heavy metals indicated that there is a considerable Cd, Cu, Pb and Zn pollution, which originate from traffic and industrial activities. The IPI of these four metals ranged from 1.6 to 11.8 with a mean of 3.5, with the highest IPI in the industrial area. The assessment results of I _geo also supported that urban soil were moderately contaminated with Cd and to a lesser extent also with Cu, Pb and Zn. The IP and I _geo values reveal the pollution degree of heavy metal was the order of Cd > Pb > Zn ≈ Cu. It was shown that mobility and bioavailability of the heavy metals in urban soils increased in the order of Cd > Cu > Zn ≈ Pb. Owing to high mobility of Cd and Cu in the urban soils, further investigations are needed to understand their effect on the urban environment and human health. It is concluded that industrial activities and emissions from vehicles may be the major source of heavy metals in urban contamination. Results of this study present a rough guide about the distribution and potential environmental and health risk of heavy metals in the urban soils.     

Compound-specific chlorine isotope ratios of TCE,PCE and DCE isomers by direct injection using CF-IRMS

A method for determining compound-specific Cl isotopic compositions (δ³⁷Cl) was developed for tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE), trans-dichloroethene (trans-DCE) and 1,1-dichloroethene (1,1-DCE). The isotope ratio mass spectrometry (IRMS) used in this study has nine collectors, including two for m/z 50 and 52 (CH₃Cl) and two for m/z 94 and 96 (CH₃Br). The development of this method is based on the fact that fragments with mass ratios of 94/96, 95/97 and 96/98 are produced from PCE, TCE and DCE isomers during ion bombardment in the source of a mass spectrometer. Using continuous flow isotope ratio mass spectrometry coupled with gas chromatography (GC–CF-IRMS), it is possible to separate these compounds on-line and directly measure the Cl isotopic ratios of the fragments with the specific mass ratios.Both pure phase and aqueous samples were used for Cl isotopic analysis. For pure phase samples, a vapour phase of the chlorinated ethenes was injected directly into the GC, whereas the solid phase micro extraction (SPME) method was used to extract these compounds from aqueous solutions. The precisions of this analytical technique were ±0.12‰ (1σ, n = 30), ±0.06‰ (1σ, n = 30), and ±0.08‰ (1σ, n = 15) for PCE, TCE and DCE isomers, respectively. The limits of quantification (LOQ) for analyzing Cl isotopic composition in aqueous solutions were 20, 5, and 5 μg/L for PCE, TCE and DCE isomers, respectively. This corresponds to 6–9 nano-mole of Cl, which is approximately 80 times lower than the most sensitive existing method. Compared to methods previously available, this new development offers the following advantages: (1) The much lower LOQ make it possible to extract these compounds directly from aqueous solutions using SPME without pre-concentration; (2) The linking of a GC with an IRMS eliminates off-line separation; and (3) Because the fragments used for isotopic ratio measurement are produced during ion bombardment in the mass spectrometer, there is no need to convert chlorinated ethenes to methyl chloride. As a result, this technique greatly enhances the efficiency for isotopic analysis by eliminating procedures for pre-concentration, off-line separation and sample preparation. In addition, it also reduces the potential for isotopic fractionation introduced during these procedures.Compound-specific Cl stable isotope analysis can be used as a tool to study the sources of organic contaminants in groundwater and their behaviour in the subsurface environments. It may also assist in understanding processes such as transport, mixing, and degradation reactions.     

Arsenic and other drinking water quality issues,Muzaffargarh District,Pakistan

In 49 samples of groundwater, sampled in Muzaffargarh District of south-western Punjab, central Pakistan, concentrations of As exceeded the World Health Organisation provisional guideline value, and United States Environmental Protection Agency (USEPA) Maximum Contaminant Level (MCL), of 10 μg L⁻¹ in 58% of samples and reached up to 906 μg L⁻¹. In this semi-arid region canal irrigation has lead to widespread water-logging, and evaporative concentration of salts has the potential to raise As concentrations in shallow groundwater well above 10 μg L⁻¹. In fact, in rural areas, concentrations stay below 25 μg L⁻¹ because As in the oxic shallow groundwater, and in recharging water, is sorbed to aquifer sediments. In some urban areas, however, shallow groundwater is found to contain elevated levels of As. The spatial distribution of As-rich shallow groundwater indicates either direct contamination with industrial or agricultural chemicals, or some other anthropogenic influence. Geochemical evidence suggests that pollutant organics from unconfined sewage and other sources drives reduction of hydrous ferric oxide (HFO) releasing sorbed As to shallow groundwater. The situation is slightly less clear for seven wells sampled which tap deeper groundwater, all of which were found with >50 μg L⁻¹ As. Here As concentrations seem to increase with depth and differing geochemical signatures are seen, suggesting that As concentrations in older groundwater may be governed by different processes. Other data on parameters of potential concern in drinking water are discussed briefly at the end of the paper.     

Assessment of natural attenuation of aromatic hydrocarbons in groundwater near a former manufactured-gas plant, South Carolina, USA

 Shallow, anaerobic groundwater near a former manufactured-gas plant (MGP) in Charleston, South Carolina, USA, contains mono- and polycyclic aromatic hydrocarbons (MAHs and PAHs, respectively). Between 1994 and 1997, a combination of field, laboratory, and numerical-flow and transport-model investigations were made to assess natural attenuation processes affecting MAH and PAH distributions. This assessment included determination of adsorption coefficients (K _ad ) and first-order biodegradation rate constants (K _bio ) using aquifer material from the MGP site and adjacent properties. Naphthalene adsorption (K _ad =1.35×10^–7 m³/mg) to aquifer sediments was higher than toluene adsorption (K _ad =9.34×10^–10 m³/mg), suggesting preferential toluene transport relative to naphthalene. However, toluene and benzene distributions measured in January 1994 were smaller than the naphthalene distribution. This scenario can be explained, in part, by the differences between biodegradation rates of the compounds. Aerobic first-order rate constants of ¹⁴C-toluene, ¹⁴C-benzene, and ¹⁴C-naphthalene degradation were similar (–0.84, –0.03, and 0.88 day^–1, respectively), but anaerobic rate constants were higher for toluene and benzene (–0.002 and –0.00014 day^–1, respectively) than for naphthalene (–0.000046 day^–1). Both areal and cross-sectional numerical simulations were used to test the hypothesis suggested by these rate differences that MAH compounds will be contained relative to PAHs. Predictive simulations indicated that the distributions of toluene and benzene reach steady-state conditions before groundwater flow lines discharge to an adjacent surface-water body, but do discharge low concentrations of naphthalene. Numerical predictions were "audited" by measuring concentrations of naphthalene, toluene, and benzene at the site in early 1997. Measured naphthalene and toluene concentrations were substantially reduced and the areal extent of contamination smaller than was both observed in January 1994 and predicted for 1997. Measured 1997 benzene concentrations and distribution were shown to be relatively unchanged from those measured in 1994, and similar to predictions for 1997. Received: 26 June 1997 · Accepted: 25 August 1997     

Hydrochemical evidence of the depth of penetration of anthropogenic recharge in sandstone aquifers underlying two mature cities in the UK

Pollution of urban groundwater is routinely reported but the profile of contamination with depth in urban aquifers is rarely resolved. This limits understanding of the depth of penetration of urban recharge and contaminants, and use of urban groundwater. Penetration of anthropogenic solutes (major ions, trace metals) in Permo-Triassic sandstone aquifers underlying two mature conurbations in the UK was investigated through depth-specific, groundwater sampling of dedicated multilevel piezometers. Identification of solute origin and biogeochemical processes (e.g. denitrification, mineral dissolution) was aided by use of stable isotope ratios (³⁴S/³²S, ¹⁸O/¹⁶O, ¹⁵N/¹⁴N, ¹³C/¹²C) and chemical speciation modelling (PHREEQC). Depth profiles of aquifer hydrochemistry reveal penetration of anthropogenic solutes to depths of between 30 and 47 m below ground in the unconfined sandstone and confirm the contributions of faecal and industrial effluents to urban recharge. They also highlight the complexity of solute loading and difficulty resolving solute origin from the range of potential sources in urban groundwater. Faecally-derived NO₃ is the most pervasive contaminant exceeding drinking-water quality guidelines and is associated with elevated concentrations of B and SO₄. Elevated concentrations of Li, B, Cr and Co are observed at depth in groundwater contaminated by long-term industrial land use (metalworking). Observed penetration of anthropogenic solutes in the unconfined sandstone is consistent with post-development recharge of urban groundwater (residence times <230 a) indicated by flow modelling, and suggests tentatively that urban abstraction to depths of up to 50 m below ground in the unconfined Permo-Triassic sandstone is required to scavenge contaminated groundwater.     

Hydrogeologic investigations of contaminant movement in karst aquifers in the vicinity of a train derailment near Lewisburg,Tennessee

A train derailment near Lewisburg, Tennessee, in October 1990 prompted two series of groundwater investigations. The first was to determine the subsurface flow route of chloroform and styrene that sank into the underlying karst aquifer. The second was to determine the source of contamination for two nearby residential wells which were found to be contaminated with trichloroethylene (TCE). Water-sample analysis and a dye trace performed at the time of the train derailment indicated groundwater flow to Wilson Spring. A dam was constructed to contain the entire discharge from the spring so that it could be treated before being discharged into Big Rock Creek. Three springs and three water wells were contaminated with chloroform and styrene. Dye traces were performed to determine groundwater flow directions in the vicinities of the TCE-contaminated wells and in the vicinities of potential sources. At the train derailment, the chloroform and styrene sank into the Upper Ridley Karst Aquifer and pooled on top of the Lower Ridley Confining Layer. An exploratory well revealed a layer of chloroform (a Dense Non-Aqueous Phase Liquid DNAPL) on the bottom, a layer of groundwater in the middle, and a layer of styrene (a Light Non-Aqueous Phase Liquid LNAPL) on top. Groundwater with relatively low levels of chloroform and styrene in solution was carried by a small cave stream southeast along the strike to Wilson Spring. Chloroform product moved by gravity southwest down-dip along weathered bedding planes. Treatment of contaminated groundwater from Wilson Spring and recovery wells at the spill site has occurred continuously since October, 1990.     

Mobilization and transport of organic compounds from reservoir rock and caprock in geological carbon sequestration sites

Supercritical CO₂ (scCO₂) is a good solvent for organic compounds such as benzene, toluene, ethyl-benzene, and xylene (BTEX), phenols, and polycyclic aromatic hydrocarbons (PAHs). Monitoring results from geological carbon sequestration (GCS) field tests have shown that organic compounds are mobilized following CO₂ injection. Such results have raised concerns regarding the potential for groundwater contamination by toxic organic compounds mobilized during GCS. Knowledge of the mobilization mechanism of organic compounds and their transport and fate in the subsurface is essential for assessing risks associated with GCS. Extraction tests using scCO₂ and methylene chloride (CH₂Cl₂) were conducted to study the mobilization of volatile organic compounds (VOCs, including BTEX), the PAH naphthalene, and n-alkanes by scCO₂ from representative reservoir rock and caprock obtained from depleted oil reservoirs and coal from an enhanced coal-bed methane recovery site. Results showed that the extent of mobilization for the organic compounds was a function of the source rock. In fate and transport sand column experiments, moisture content was found to have an important influence on the transport of the organic compounds. In dry sand columns the majority of the compounds were retained in the column except benzene and toluene. In wet sand columns the mobility of the BTEX was much higher than that of naphthalene. Based upon the results determined for the reservoir rock, caprock, and coal samples studied here, the risk to aquifers from contamination by organic compounds appears to be relatively low; however, further work is necessary to fully evaluate the risks.     

四氯乙烯在不同地下水环境的生物共代谢降解

四氯乙烯是地下水中常见的污染物,采用生物方法进行处理的优点是可以实现无害化、无二次污染、处理成本低。四氯乙烯只能在厌氧条件下发生还原脱氯,目前对产甲烷环境下四氯乙烯的降解研究较多,而对较弱还原环境,如反硝化、铁锰还原和硫酸盐还原环境下四氯乙烯的脱氯行为研究甚少。本文采用批实验,研究了在不同地下水环境,包括反硝化、铁还原、硫酸盐还原、混合电子受体和天然地下水环境下四氯乙烯的脱氯性能。结果表明,铁还原环境的四氯乙烯脱氯效果最好,天然地下水环境次之,四氯乙烯的去除率分别达到91.34%和84.71%,四氯乙烯很快转化为三氯乙烯,并可以进一步转化为二氯乙烯,四氯乙烯的降解符合准一级反应动力学方程。在反硝化、硫酸盐还原、混合电子受体环境,四氯乙烯的去除以挥发为主,降解只占很小的比例,且最终的降解产物只有三氯乙烯。地下水中三价铁的存在,对于四氯乙烯脱氯起促进作用;而当地下水中硝酸盐和硫酸盐的浓度较高时,四氯乙烯脱氯受到抑制。     

Concentration distribution and assessment of heavy metals in sediments of mud area from inner continental shelf of the East China Sea

Heavy metals (Cr, Cu, Zn, Cd, Pb, Hg, and As), grain-size, pH, Eh, and total organic material (TOM and TN) of 59 surficial sediments of mud area from the inner continental shelf of the East China Sea have been analyzed. The relations of the heavy metals to sediment composition, pH, reduction/oxidation conditions and total organic materials were evaluated with multivariate statistics analysis, and the hydrodynamic conditions such as coastal current and Taiwan warm current are the other important controlling factors to the distribution of heavy metals. Sediment enrichment factors and potential ecological hazard index ( E_\textRI E_{\text{RI}} ) were used to assess the heavy metals accumulation; the results indicate that moderate contamination of most heavy metals is prevalent, and the contamination level in the estuary is rather high, which is mainly from anthropogenic source. Compared with other areas in China, the contaminant level of the study area is moderate.     

Processes affecting geochemistry and contaminant movement in the middle Claiborne aquifer of the Mississippi embayment aquifer system

Groundwater chemistry and tracer-based age data were used to assess contaminant movement and geochemical processes in the middle Claiborne aquifer (MCA) of the Mississippi embayment aquifer system. Water samples were collected from 30 drinking-water wells (mostly domestic and public supply) and analyzed for nutrients, major ions, pesticides, volatile organic compounds (VOCs), and transient age tracers (chlorofluorocarbons, tritium and helium-3, and sulfur hexafluoride). Redox conditions are highly variable throughout the MCA. However, mostly oxic groundwater with low dissolved solids is more vulnerable to nitrate contamination in the outcrop areas east of the Mississippi River in Mississippi and west Tennessee than in mostly anoxic groundwater in downgradient areas in western parts of the study area. Groundwater in the outcrop area was relatively young (apparent age of less than 40 years) with significantly (p < 0.05) higher dissolved oxygen and nitrate–N concentrations and higher detections of pesticides and VOCs compared to water samples from wells in downgradient areas. Oxygen reduction and denitrification rates were low compared to other aquifers in the United States (zero order rate constants for oxygen reduction and denitrification were 4.7 and 5–10 μmol/L/year, respectively). Elevated concentrations of nitrate–N, and detections of pesticides and VOCs in some deep public supply wells (>50 m depth) indicated contaminant movement from shallow parts of the aquifer into deeper oxic zones. Given the persistence of nitrate in young oxic groundwater that was recharged several decades ago, and the lack of a confining unit, the downward movement of young contaminated water may result in higher nitrate concentrations over time in deeper parts of the aquifer containing older oxic water.     

Source partitioning of anthropogenic groundwater nitrogen in a mixed-use landscape,Tutuila, American Samoa

This study presents a modeling framework for quantifying human impacts and for partitioning the sources of contamination related to water quality in the mixed-use landscape of a small tropical volcanic island. On Tutuila, the main island of American Samoa, production wells in the most populated region (the Tafuna-Leone Plain) produce most of the island’s drinking water. However, much of this water has been deemed unsafe to drink since 2009. Tutuila has three predominant anthropogenic non-point-groundwater-pollution sources of concern: on-site disposal systems (OSDS), agricultural chemicals, and pig manure. These sources are broadly distributed throughout the landscape and are located near many drinking-water wells. Water quality analyses show a link between elevated levels of total dissolved groundwater nitrogen (TN) and areas with high non-point-source pollution density, suggesting that TN can be used as a tracer of groundwater contamination from these sources. The modeling framework used in this study integrates land-use information, hydrological data, and water quality analyses with nitrogen loading and transport models. The approach utilizes a numerical groundwater flow model, a nitrogen-loading model, and a multi-species contaminant transport model. Nitrogen from each source is modeled as an independent component in order to trace the impact from individual land-use activities. Model results are calibrated and validated with dissolved groundwater TN concentrations and inorganic δ¹⁵N values, respectively. Results indicate that OSDS contribute significantly more TN to Tutuila’s aquifers than other sources, and thus should be prioritized in future water-quality management efforts.     

Detection of nitrate sources in urban groundwater by isotopic and chemical indicators,Hangzhou City,China

The sources of nitrate in the shallow groundwater at urban area, Hangzhou City, China were investigated using chemical and isotopic techniques. Groundwater electric conductivity was high in the study area and ranged from 369–1,544 S/cm. Most of the groundwater was weakly alkaline and the groundwater chemistry was seriously influenced by land use in the city. There was a high frequency of groundwater (43% of total) with nitrate above World Heath Organizations standards of 10 mg NO₃/L. The different land-use areas had different nitrate concentrations (0.04–34.41 mgN/L) and ¹⁵N _NO3 values (7.8~35.5). Domestic wastewater was the major nitrate source of shallow groundwater in the urban area, and the point source (septic tank) still existed in residential settings. At agricultural settings manure was the major NO₃ sources. High ¹⁵N _NO3 value (>20) and temporal variations of the ¹⁵N _NO3 value suggested that in residential areas it probably resulted from denitrification.     

Microbial degradation of chloroethenes in groundwater systems

The chloroethenes, tetrachloroethene (PCE) and trichloroethene (TCE) are among the most common contaminants detected in groundwater systems. As recently as 1980, the consensus was that chloroethene compounds were not significantly biodegradable in groundwater. Consequently, efforts to remediate chloroethene-contaminated groundwater were limited to largely unsuccessful pump-and-treat attempts. Subsequent investigation revealed that under reducing conditions, aquifer microorganisms can reductively dechlorinate PCE and TCE to the less chlorinated daughter products dichloroethene (DCE) and vinyl chloride (VC). Although recent laboratory studies conducted with halorespiring microorganisms suggest that complete reduction to ethene is possible, in the majority of groundwater systems reductive dechlorination apparently stops at DCE or VC. However, recent investigations conducted with aquifer and stream-bed sediments have demonstrated that microbial oxidation of these reduced daughter products can be significant under anaerobic redox conditions. The combination of reductive dechlorination of PCE and TCE under anaerobic conditions followed by anaerobic microbial oxidation of DCE and VC provides a possible microbial pathway for complete degradation of chloroethene contaminants in groundwater systems. Résumé Les chloroéthanes, tétrachloroéthane (PCE) et trichloroéthane (TCE) sont parmi les polluants les plus communs trouvés dans les aquifères. Depuis les années 1980, on considère que les chloroéthanes ne sont pas significativement biodégradables dans les aquifères. Par conséquent, les efforts pour dépolluer les nappes contaminées par des chloroéthanes se sont limités à des tentatives de pompage-traitement globalement sans succès. Des travaux ultérieurs ont montré que dans des conditions réductrices, des micro-organismes présents dans les aquifères peuvent, par réduction, dégrader les PCE et TCE en composés moins chlorés, comme le dichloréthane (DCE) et le chlorure de vinyl (VC). Bien que des études de laboratoire réalisées avec des micro-organismes adaptés aux composés halogénés montrent que la réduction complète en éthane est possible, dans la plupart des nappes la réaction de déchloration par réduction s'arrête apparemment au DCE et au VC. Cependant, des recherches récentes menées sur des sédiments d'un aquifère et d'alluvions ont démontré que l'oxydation microbienne de ces descendants réduits peut se produire de manière significative dans des conditions de redox anérobies. La déchloration par réduction de PCE et de TCE dans des conditions anérobies suivie par une oxydation microbienne anérobie des DCE et VC fournit une piste microbienne possible pour obtenir une dégradation complète des chloroéthanes polluants dans les aquifères. Resumen Los cloroetanos (tetracloroetano PCE y tricloroetano TCE) son contaminantes muy habituales en los acuíferos. Hasta 1980 se consideraba que los cloroetanos no eran biodegradables y, por tanto, los métodos de rehabilitación en acuíferos contaminados con cloroetanos se limitaban al pump-and-treat, generalmente con poco éxito. Posteriormente se vio que, en condiciones reductoras, algunos microorganismos pueden reducir PCE y TCE a unos subproductos menos clorados, como el dicloroetano (DCE) y el cloruro de vinilo (VC). Aunque estudios de laboratorio recientes sugieren que la reducción completa a etano es posible, en la mayoría de los sistemas acuíferos la decloración suele detenerse en los DCE o VC. Sin embargo, investigaciones más recientes en acuíferos y sedimentos fluviales demuestran que la oxidación microbiana de estos subproductos puede ser importante bajo condiciones redox anaerobias. La combinación de la reducción de PCE y TCE en condiciones anaerobias seguida de la oxidación microbiana anaerobia de DCE y VC proporciona un método potencial para la degradación total de los cloroetanos en los sistemas acuíferos.     

Geochemical assessment and speciation of metals in sediments of Osun and Erinle Rivers,Southwestern Nigeria

Fifty sediment samples were collected from Osun (urban) and Erinle (suburban) rivers in addition to ten samples of the underlying rock types (schist and gneiss) and analyzed for elemental constituents while speciation of metals was determined by sequential analysis. Data were geochemically evaluated and ArcGIS was used to generate geochemical maps. Metal concentrations (ppm) in sub-urban and urban areas were Cd (0.2–0.2, 0.2–1.1), Cu (37.0–272.0, 49.0–970.0), Ni (6.0–27.0, 3.0–43.0), Pb (16.0–67.0, 15.0–2650.0), Zn (32.0–170.0, 50.0–987.0), Co (8.0–60.0, 2.0–86.0), Cr (26.0–153.0, 9.0–128.0), V (30.0–142.0, 9.0–135.0), and Mn (442.0–5100.0, 107.0–3930.0), respectively. In the rocks, Cu, Ni, Pb, Co, Cr, V, and Zn, concentrations (ppm) were below detection limit (BDL)-0.05, BDL-38.00; 6.23–12.00, BDL-20.00; 3.78–6.23, BDL-5.00; BDL-0.20, BDL-4.00; 5.00–9.00, BDL-66.00; 15.99–32.00, BDL-130.00; and 18.00–26.00, BDL-48.00, respectively, with Cu, Pb, Zn, Cd, and Mn of elevated concentrations in sediments compared with that of the rocks, being indication of additional anthropogenic sourcing. Calculated contamination indices revealed contamination for sediment from the urban areas compared to those from the sub-urban. High percentage of Pb (2.94–81.92%), Cu (31.69–45.95%), Zn (49.2–65.5%), Cd (31.69–45.95%), and Mn (12.13–37.50%) are hosted by the bio-available phases (carbonate, organic, and sulfide). The geochemical distribution of metals in the sediments of the Osun and Erinle rivers is governed by both geogenic (Ni-Cr-Co-V) and anthropogenic (Pb-Cd-Zn) activities. Elevated concentration and occurrences of the selected metals in the bio-available phases pose potential health risk to people in the urban area.