Geochemistry of high arsenic groundwater in Chia-Nan plain, Southwestern Taiwan: possible sources and reactive transport of arsenic

Major ion, trace element, and stable isotope analyses were performed on groundwater samples collected during November 2005 and 2006 in Chia-Nan plain of southwestern Taiwan to examine As mobilization in aquifers. The high concentrations of As, Fe and Mn in the groundwater is consistent with low Eh values (under moderately reduced state). Moreover, the observed Na/Cl and SO(4)/Cl molar ratios in groundwater demonstrate the influence of seawater intrusion. Seawater intrusion could provide required electron acceptors (i.e., SO(4)) for bacterial sulfate reduction and promote reducing conditions that are favorable for As mobilization. The concurrent increases in the concentrations of Fe and Mn from 2005 to 2006 may be caused by bacterial Fe(III) and Mn(IV) reduction. Geochemical modeling demonstrate that As(III) is the dominant As species and the presence of Fe-bearing carbonates, sulfides, and oxide phases may locally act as potential sinks for As. Mud volcano fluids were also collected and analyzed to assess the possible source of As in the Chia-Nan plain groundwater. The oxygen and hydrogen isotopic signatures indicate that the As-rich mud volcano fluids may have been modified by chemical exchange with (18)O-rich crustal rocks and possibly originated from mixing of deep brines with circulating meteoric water. Thus As in the Chia-Nan plain groundwater may have been evolved from deep crustal fluids or rock sources. The hydrogeochemistry and widespread As enrichment in groundwater of Chia-Nan plain result from multiple processes, e.g., de-watering of deep crustal fluids, seawater intrusion, and biogeochemical cycling of Fe, As, and S in alluvial sediments.     

Assessing the chemical behavior and spatial distribution of yttrium and rare earth elements (YREEs) in a coastal aquifer adjacent to the Urmia Hypersaline Lake,NW Iran

This study aims to shed light on the seasonal behavior of yttrium and rare earth elements (YREEs) in the Urmia Aquifer (UA), in the immediate vicinity of Urmia Lake (UL) in Iran. Samples of groundwater, collected under dry and wet conditions in coastal wells of UA, suggest a large degree of variability in both YREE abundance and normalized patterns. Although weathering or water-rock interactions (between the surface/groundwater and rock samples) were predicted to be the most probable source in explaining YREEs in groundwater samples, results to the contrary indicate that the groundwater do not inherit aquifer rock-like YREE signatures in the study area; this might be due to the relative stability of YREEs during the process of water-rock interactions, which suggest that methods based on YREEs can be beneficial in discrimination of water sources. Furthermore, findings demonstrated no significant relationship between Ce/Ce* and salinity (0.08 and 0.05 in wet and dry seasons, respectively), and between Eu/Eu* and salinity (0.1 and ?0.04 in wet and dry seasons, respectively). Dissimilarity of patterns of YREEs in rock and water samples reveals YREEs as no conservative tracers in determining the UL saltwater intrusion into coastal groundwater. Therefore, the groundwater YREE concentrations and fractionation patterns in UA warrant controlling by coastal aquifer need to be controlled by other chemical weathering, adsorption, desorption, and solution complexation reactions. Finally, comparison of REE concentration values in groundwater samples with corresponding indicative admissible drinking water concentrations (IAC) demonstrated their suitability for drinking purposes.

     

Hydrochemical and multivariate statistical interpretations of spatial controls of nitrate concentrations in a shallow alluvial aquifer around oxbow lakes (Osong area, central Korea)

Hydrochemical and multivariate statistical interpretations of 16 physicochemical parameters of 45 groundwater samples from a riverside alluvial aquifer underneath an agricultural area in Osong, central Korea, were performed in this study to understand the spatial controls of nitrate concentrations in terms of biogeochemical processes occurring near oxbow lakes within a fluvial plain. Nitrate concentrations in groundwater showed a large variability from 0.1 to 190.6 mg/L (mean = 35.0 mg/L) with significantly lower values near oxbow lakes. The evaluation of hydrochemical data indicated that the groundwater chemistry (especially, degree of nitrate contamination) is mainly controlled by two competing processes: 1) agricultural contamination and 2) redox processes. In addition, results of factorial kriging, consisting of two steps (i.e., co-regionalization and factor analysis), reliably showed a spatial control of the concentrations of nitrate and other redox-sensitive species; in particular, significant denitrification was observed restrictedly near oxbow lakes. The results of this study indicate that sub-oxic conditions in an alluvial groundwater system are developed geologically and geochemically in and near oxbow lakes, which can effectively enhance the natural attenuation of nitrate before the groundwater discharges to nearby streams. This study also demonstrates the usefulness of multivariate statistical analysis in groundwater study as a supplementary tool for interpretation of complex hydrochemical data sets.     

Assessment of pesticide contamination in Akkar groundwater,northern Lebanon

According to its high production and value, Akkar is considered as the second agricultural region in Lebanon. Groundwater constitutes the principal source of water in Akkar including drinking water of local inhabitants in Akkar. As such, the contamination of groundwater by organic pollutants can impact directly the population health. In this study, we evaluated the contamination status of groundwater in this region. Three classes of pesticides including 19 organochlorine (OC) pesticides, 8 organophosphorus (OP) pesticides, and 6 organonitrogen (ON) pesticides were monitored in 15 groundwater samples collected from different villages on the Akkar plain. Samples were extracted by using solid phase extraction (SPE) and analyzed by gas chromatography coupled with mass spectrometry (GC-MS). The results showed high contamination of Akkar groundwater by OCs with levels that can reach 58.9 μg/L. They were detected in the majority of the sample and represent 95–100% of ∑pesticides. Our results showed the recent use of these molecules with an average level of 0.3 and 0.39 μg/L for ∑HCHs and DDTs, respectively. Their concentrations were higher than those observed in the same region in 2014 and other regions elsewhere. OPs were also detected at high levels and among them, methylparathion was the predominant OP detected (44.6 μg/L). For ONs, lower levels were measured in all samples with a mean value of 5.6 μg/L. As a conclusion of this work, groundwater on the plain of Akkar was remarkably contaminated by the studied pesticides; indefinitely, more efforts should be taken to manage the pesticide use in this region, assess, and reduce their effects on human health. In the future, the application of organic farming can be a great solution to the groundwater contamination problem.     

Herbicide leaching on a recharge area of the Guarany aquifer in Brazil

The region of Ribeir?o Preto City, located in Southeast of Brazil, S?o Paulo State, is an important sugarcane, soybean, and corn producing area with a high level of pesticides utilization. This region is also an important recharge area for groundwater supply of the Guarany aquifer. Since the past ten years atrazine, simazine, ametryn, tebuthiuron, diuron, 2,4-D, picloram, and hexazinone are the main herbicides used in this area. In order to study a possible leaching of some of these herbicides into the aquifer, surface, and groundwater samples were collected in a watershed during the years of 1996 to 2003, from different locations. To detect and quantify the herbicides a GC-MS (gas chromatograph/mass spectrometry) method was used. The response of the herbicides analyzed was linear over the concentration range of 0.02 to 2.0 microg/L. Analysis of groundwater revealed that the herbicides tebuthiuron, diuron, atrazine, simazine, and ametryn were not present in the samples. In the surface water collected in 1997, ametryn was present in two out of nine locations with concentrations ranging from 0.17 and 0.23 microg/L, which is above the allowable 0.1 microg/L according to the European safety level. The leaching potential of tebuthiuron, diuron, atrazine, simazine, 2,4-D, picloram, and hexazinone has been evaluated using CMLS-94, "Chemical Movement in Layered Soil," as simulation model. No leaching into the depth of the water table at 40 m was found.     

Herbicide Leaching on a Recharge Area of the Guarany Aquifer in Brazil

Abstract

The region of Ribeirão Preto City, located in Southeast of Brazil, São Paulo State, is an important sugarcane, soybean, and corn producing area with a high level of pesticides utilization. This region is also an important recharge area for groundwater supply of the Guarany aquifer. Since the past ten years atrazine, simazine, ametryn, tebuthiuron, diuron, 2,4-D, picloram, and hexazinone are the main herbicides used in this area. In order to study a possible leaching of some of these herbicides into the aquifer, surface, and groundwater samples were collected in a watershed during the years of 1996 to 2003, from different locations. To detect and quantify the herbicides a GC-MS (gas chromatograph/mass spectrometry) method was used. The response of the herbicides analyzed was linear over the concentration range of 0.02 to 2.0 μg/L. Analysis of groundwater revealed that the herbicides tebuthiuron, diuron, atrazine, simazine, and ametryn were not present in the samples. In the surface water collected in 1997, ametryn was present in two out of nine locations with concentrations ranging from 0.17 and 0.23 μg/L, which is above the allowable 0.1 μg/L according to the European safety level. The leaching potential of tebuthiuron, diuron, atrazine, simazine, 2,4-D, picloram, and hexazinone has been evaluated using CMLS-94, “Chemical Movement in Layered Soil,” as simulation model. No leaching into the depth of the water table at 40 m was found.     

Sources of fluorescent dissolved organic matter in high salinity seawater (Bohai Bay, China)

Fluorescent dissolved organic matter (FDOM) identified in coastal waters within a large salinity range had been widely reported in previous studies, which stated that conservative mixing of terrestrially derived and river-transported FDOM by clear seawaters could account for the relatively low FDOM fluorescence signals in high salinity seawaters. This study aimed at testing the conservative mixing model in high salinity seawaters in a shallow bay (Bohai Bay, China) with low river flow in a dry season. The water showed high salinities varying in a narrow range (30.52???2.07), and salinity effects on fluorescence quantum yields therefore less likely introduced complications to fluorescence data analyses. By applying a parallel factor analysis to fluorescence excitation emission matrices of the water samples, we identified a tyrosine-like FDOM component, a tryptophan-like FDOM component, and two humic substances-like FDOM components. Based on a theoretical analysis, we found that dissolved organic carbon concentrations and suspended solid concentrations of the bulk-water samples as well as the maximum fluorescence signals of each identified FDOM component showed spatial distributions that could not be accounted for by the conservative mixing model. Marine autochthonous processes including microbial activities and FDOM releasing from resuspended sediment were likely to be invoked.     

Groundwater quality assessment and pollution source apportionment in an intensely exploited region of northern China

Deterioration in groundwater quality has attracted wide social interest in China. In this study, groundwater quality was monitored during December 2014 at 115 sites in the Hutuo River alluvial-pluvial fan region of northern China. Results showed that 21.7% of NO₃ ^? and 51.3% of total hardness samples exceeded grade III of the national quality standards for Chinese groundwater. In addition, results of gray relationship analysis (GRA) show that 64.3, 10.4, 21.7, and 3.6% of samples were within the I, II, IV, and V grades of groundwater in the Hutuo River region, respectively. The poor water quality in the study region is due to intense anthropogenic activities as well as aquifer vulnerability to contamination. Results of principal component analysis (PCA) revealed three major factors: (1) domestic wastewater and agricultural runoff pollution (anthropogenic activities), (2) water-rock interactions (natural processes), and (3) industrial wastewater pollution (anthropogenic activities). Using PCA and absolute principal component scores-multivariate linear regression (APCS-MLR), results show that domestic wastewater and agricultural runoff are the main sources of groundwater pollution in the Hutuo River alluvial-pluvial fan area. Thus, the most appropriate methods to prevent groundwater quality degradation are to improve capacities for wastewater treatment and to optimize fertilization strategies.     

Contamination by arsenic and other trace elements in tube-well water and its risk assessment to humans in Hanoi, Vietnam

Concentrations of As and other trace elements and their association were examined in groundwater (n = 25) and human hair (n = 59) collected at Gia Lam District and Thanh Tri District, suburban areas of Hanoi, Vietnam, in September 2001. Concentrations of As in the groundwater ranged from <0.10 to 330 microg/l, with about 40% of these exceeding WHO drinking water guideline of 10 microg/l. Also, 76% and 12% of groundwater samples had higher concentrations of Mn and Ba than WHO drinking water guidelines, respectively. Arsenic concentrations in hair of residents in Gia Lam and Thanh Tri Districts (range 0.088-2.77 microg/g dry wt.) were lower than those in other As-contaminated areas of the world, but were higher than those of people in non-contaminated areas. Concentrations of As and Mn in hair of some individuals from the Gia Lam and Thanh Tri Districts exceeded the level associated with their toxicity and, therefore, a potential health risk of As and Mn is a concern for the people consuming the contaminated water in this area. Cumulative As exposure was estimated to be lower than the threshold levels at the present, which might explain the absence of manifestations of chronic As poisoning and arsenicosis in the residents of Gia Lam and Thanh Tri Districts. To our knowledge, this study revealed for the first time that the residents are exposed not only to As but also Mn and Ba from groundwater in the Red River Delta, Vietnam.     

Impact of urbanization on hydrochemical evolution of groundwater and on unsaturated-zone gas composition in the coastal city of Tel Aviv, Israel

The coastal city of Tel Aviv was founded at the beginning of the 20th century. The number of its inhabitants and its water consumption increased rapidly. This study analyses a 15-year record (1934-1948) of pre-industrial development of groundwater chemistry in the urban area. Archive data on concentrations of major ions, dissolved gases (CO2 and O2), organic matter, and pH were available for each half-year during the period of 1934-1948. The major factors causing changes in the chemistry of groundwater flowing in three sandy sub-aquifers have been seawater encroachment due to overpumping, and infiltration of effluents from pit-latrine collectors. Influence of these factors decreases with depth. Landward-penetrating seawater passed through clayey coastal sediments, interbedded among sands and calcareous sandstones, and spread into the Kurkar Group aquifer. This has led to exchange of sodium (dominant in seawater) with calcium adsorbed on clay particles, enriching groundwater with calcium. Intensity of cation exchange decreases inland and with depth. Infiltration of pit-latrine effluents has introduced large amounts of ammonium into the unsaturated zone. Its rapid oxidation in unsaturated sediments has caused massive nitrate production, accompanied by pore-water acidification. This process induces dissolution of vadose carbonate, resulting in enrichment of groundwater recharge in calcium. Anthropogenically induced dissolution of calcite in the unsaturated zone has been the major factor for the increase of Ca2+ concentration in groundwater, accounting for about 80% of this increase. In the interface zone, an additional 20% of calcium has been supplied by cation exchange. Owing to pH increase caused by denitrification in the aquifer, Ca(2+)-rich waters supersaturated with calcite could be formed, especially in the capillary fringe of the uppermost sub-aquifer, which could induce calcite precipitation and ultimately lead to the cementation of sandy aquifers. Urban development has caused drastic changes in the gas content in the unsaturated zone and in groundwater. Carbon dioxide was intensively generated by nitrification-denitrification processes, by hydration of urea, to a lesser degree by oxidation of organic matter, and probably by anoxic biodegradation of organics. Between 1934 and 1948, concentrations of CO2 in unsaturated sediment air rose from 3.2% to 7.6%. In the unsaturated zone, oxygen consumption for oxidation of ammonium and organic matter lowered O2 concentrations in sediment air to unusually low values of 3.9-12.9%. Nitrification in the urban unsaturated zone could thus serve as a pump, sucking in atmospheric oxygen at a rate of about 0.3-0.5 g m-2 day-1. The extreme concentrations of CO2 and O2 in unsaturated sediments have been preserved due to production and consumption of gas under conditions of diminishing areas open to the atmosphere, uncovered by buildings and by roads.     

Trends in nitrate concentrations and determination of its origin using stable isotopes (18O and 15N) in groundwater of the Western Central Valley, Costa Rica

A study was conducted to evaluate long-term trends in nitrate concentrations and to try to identify the origin of nitrate using stable isotopes (15N(NO3-) and 18O(NO3-)) in the aquifers of the western Central Valley, Costa Rica, where more than 1 million people depend on groundwater to satisfy their daily needs. Data from 20 sites periodically sampled for 4 to 17 years indicate an increasing trend in nitrate concentrations at five sites, which in a period ranging from 10 to 40 years, will exceed recommended maximum concentrations. Results of isotopic analysis indicate a correspondence between land use patterns and the isotopic signature of nitrate in groundwater and suggest that urbanization processes without adequate waste disposal systems, followed by coffee fertilization practices, are threatening water quality in the region. We conclude that groundwater management in this area is not sustainable, and that land use substitution processes from agricultural activity to residential occupation that do not have proper sewage disposal systems may cause a significant increment in the nitrate contaminant load.     

Groundwater-surface water interaction and its role on TCE groundwater plume attenuation

A field investigation of a TCE plume in a surficial sand aquifer shows that groundwater-surface water interactions strongly influence apparent plume attenuation. At the site, a former industrial facility in Connecticut, depth-discrete monitoring along three cross-sections (transects) perpendicular to groundwater flow shows a persistent VOC plume extending 700 m from the DNAPL source zone to a mid-size river. Maximum TCE concentrations along a transect 280 m from the source were in the 1000s of microg/L with minimal degradation products. Beyond this, the land surface drops abruptly to a lower terrace where a shallow pond and small streams occur. Two transects along the lower terrace, one midway between the facility and river just downgradient of the pond and one along the edge of the river, give the appearance that the plume has strongly attenuated. At the river, maximum TCE concentrations in the 10s of microg/L and similar levels of its degradation product cis-DCE show direct plume discharge from groundwater to the river is negligible. Although degradation plays a role in the strong plume attenuation, the major attenuation factor is partial groundwater plume discharge to surface water (i.e. the pond and small streams), where some mass loss occurs via water-air exchange. Groundwater and stream mass discharge estimates show that more than half of the plume mass discharge crossing the first transect, before surface water interactions occur, reaches the river directly via streamflow, although river concentrations were below detection due to dilution. This study shows that groundwater and surface water concentration measurements together provide greater confidence in identifying and quantifying natural attenuation processes at this site, rather than groundwater measurements alone.     

Factors controlling groundwater quality in the Yeonjegu District of Busan City,Korea, using the hydrogeochemical processes and fuzzy GIS

The hydrogeochemical processes and fuzzy GIS techniques were used to evaluate the groundwater quality in the Yeonjegu district of Busan Metropolitan City, Korea. The highest concentrations of major ions were mainly related to the local geology. The seawater intrusion into the river water and municipal contaminants were secondary contamination sources of groundwater in the study area. Factor analysis represented the contamination sources of the mineral dissolution of the host rocks and domestic influences. The Gibbs plot exhibited that the major ions were derived from the rock weathering condition. Piper’s trilinear diagram showed that the groundwater quality was classified into five types of CaHCO₃, NaHCO₃, NaCl, CaCl₂, and CaSO₄ types in that order. The ionic relationship and the saturation mineral index of the ions indicated that the evaporation, dissolution, and precipitation processes controlled the groundwater chemistry. The fuzzy GIS map showed that highly contaminated groundwater occurred in the northeastern and the central parts and that the groundwater of medium quality appeared in most parts of the study area. It suggested that the groundwater quality of the study area was influenced by local geology, seawater intrusion, and municipal contaminants. This research clearly demonstrated that the geochemical analyses and fuzzy GIS method were very useful to identify the contaminant sources and the location of good groundwater quality.

     

Shallow groundwater quality on dairy farms with irrigated forage crops

California's dairies are the largest confined animal industry in the state. A major portion of these dairies, which have an average herd size of nearly 1000 animal units, are located in low-relief valleys and basins. Large amounts of liquid manure are generated and stored in these dairies. In the semi-arid climate, liquid manure is frequently applied via flood or furrow irrigation to forage crops that are grown almost year-round. Little is known about the impact of manure management practices on water quality of the extensive alluvial aquifers underlying these basins. The objective of this work is to assess nitrate and salt leaching to shallow groundwater in a relatively vulnerable hydrogeologic region and to quantify the impact from individual sources on dairies. The complex array of potential point and nonpoint sources was divided into three major source areas representing farm management units: (1) manure water lagoons (ponds); (2) feedlot or exercise yard, dry manure, and feed storage areas (corrals); and (3) manure irrigated forage fields (fields). An extensive shallow groundwater-monitoring network (44 wells) was installed in five representative dairy operations in the northeastern San Joaquin Valley, CA. Water quality (electrical conductivity, nitrate-nitrogen, total Kjehldahl nitrogen) was observed over a 4-year period. Nitrate-N, reduced nitrogen and electrical conductivity (EC, salinity) were subject to large spatial and temporal variability. The range of observed nitrate-N and salinity levels was similar on all five dairies. Average shallow groundwater nitrate-N concentrations within the dairies were 64 mg/l compared to 24 mg/l in shallow wells immediately upgradient of these dairies. Average EC levels were 1.9 mS/cm within the dairies and 0.8 mS/cm immediately upgradient. Within the dairies, nitrate-N levels did not significantly vary across dairy management units. However, EC levels were significantly higher in corral and pond areas (2.3 mS/cm) than in field areas (1.6 mS/cm) indicating leaching from those management units. Pond leaching was further inferred from the presence of reduced nitrogen in three of four wells located immediately downgradient of pond berms. The estimated minimum average annual groundwater nitrate-N and salt loading from manure-treated forage fields were 280 and 4300 kg/ha, respectively. Leaching rates for ponds are estimated to be on the order of 0.8 m/year, at least locally. Since manure-treated fields represent by far the largest land area of the dairy, proper nutrient management will be a key to protecting groundwater quality in dairy regions overlying alluvial aquifers.     

Toxic fluoride and arsenic contaminated groundwater in the Lahore and Kasur districts, Punjab, Pakistan and possible contaminant sources

The present study is the first attempt to put forward possible sources of As, F- and SO4(2-) contaminated groundwater in the Kalalanwala area, Punjab, Pakistan. Five rainwater and 24 groundwater samples from three different depths were analyzed. Shallow groundwater from 24 to 27 m depth contained high F- (2.47-21.1mg/L), while the groundwater samples from the deeper depth were free from fluoride contamination. All groundwater samples contained high As (32-1900 microg/L), in excess of WHO drinking water standards. The SO4(2-) ranges from 110 to 1550 mg/L. Delta34S data indicate three sources for SO4(2-) air pollutants (5.5-5.7 per thousand), fertilizers (4.8 per thousand), and household waste (7.0 per thousand). Our important finding is the presence of SO4(2-), As and F- in rainwater, indicating the contribution of these elements from air pollution. We propose that pollutants originate, in part, from coal combusted at brick factories and were mobilized promotionally by the alkaline nature of the local groundwater.     

Hydrochemical characteristics and identification of groundwater pollution sources in tropical savanna

Groundwater pollution of the watershed is mainly influenced by the multifaceted interactions of natural and anthropogenic processes. In this study, classic chemical and multivariate statistical methods were utilized to assess the groundwater quality and ascertain the potential contamination sources affecting the groundwater quality of Galma sub-watershed in a tropical savanna. For this purpose, the data set of 18 groundwater quality variables covering 57 different sampling boreholes (BH) was used. The groundwater samples essentially contained the cations in the following order of dominance: Ca²⁺ ?>?Na⁺ ?>?Mg²⁺ ?>?K⁺. However, the anions had HCO₃^–?>?Cl^–?>?SO₄^–2?>?NO₃^– respectively. The hydrochemical facies classified the groundwater types of the sub-watershed into mixed Ca–Mg–Cl type of water, which means no cations and anions exceeds 50%. The second dominant water type was Ca–Cl. The Mg–HCO₃ water type was found in BH 9, and Na–Cl water type in BH 29 of the studied area. The weathering of the basement rocks was responsible for the concentrations of these ions in the groundwater chemistry of the sub-watershed. Hierarchical cluster analysis (HCA) grouped the groundwater samples (boreholes) into five clusters that are statistically significant regarding the similarities of groundwater quality characteristics. The principal component analysis (PCA) extracted two major principal components explained around 65% of the variance and suggested the natural and anthropogenic processes especially the agricultural pollutants including synthetic fertilizers, and leaching of agricultural waste as the main factors affecting the groundwater quality. The integrated method proved to be efficient and robust for groundwater quality evaluation, as it guaranteed the precise assessment of groundwater chemistry in the sub-watershed of the tropical savanna. The findings of this investigation could be useful to the policy makers for developing effective groundwater management plans for the groundwater resources and protection of the sub-watershed.

     

Assessment of adsorption behavior of dibutyltin (DBT) to clay-rich sediments in comparison to the highly toxic tributyltin (TBT)

The sorption behavior of dibutyltin (DBT) to four types of natural clay-rich sediments as a function of pH and salinity was studied. The strongest affinity of DBT was found to the montmorillonite-rich sediment, which is characterized by the highest specific surface area and cation exchange capacity of the four used sediments. Kd values range between 12 and 40 (l/kg) on simulated marine conditions (pH 8, salinity 32%). A maximum of DBT adsorption was found at a salinity of 0% and pH 6. Desorption occurred over the entire studied pH range (4-8) when contaminated sediments interact with butyltin-free water. The maximum of desorption coincided with the minimum of adsorption, and vice versa. The results of DBT adsorption are compared with tributyltin (TBT), and the mechanism of the adsorption process is discussed.     

Behaviour and biodegradation of sulfonamides (p-TSA, o-TSA, BSA) during drinking water treatment

Three sulfonamides -para-toluenesulfonamide (p-TSA), ortho-toluenesulfonamide (o-TSA) and benzenesulfonamide (BSA) - have recently been detected in groundwater within a catchment area of one drinking water treatment plant (DWTP), which is located downstream of a former sewage farm. The degradation pathways of p-TSA, o-TSA and BSA were investigated during drinking water treatment with incubation experiments and an experimental filter. Incubation experiments showed that p-TSA is removed during the treatment by microbiological processes. Removal of p-TSA is performed by adapted microorganisms only present in polluted groundwater. The elimination in an experimental filter of 1.6m length applying filtration velocities from 2 to 6 m h(-1) was approximately 93% of p-TSA. The microbial degradation rates in the incubation experiment were approximately 0.029 microg l(-1) h(-1) (zero order reaction). In the experimental filter, the reaction rate constants were around 0.0063 s(-1) for all filtration velocities (1st order reaction). Drinking water treatment does not reduce the concentration of o-TSA and BSA under conditions encountered in Berlin. p-TSA, o-TSA and BSA were only measured in the low microg l(-1) concentrations range in the purified water.     

Dynamic factor analysis of groundwater quality trends in an agricultural area adjacent to Everglades National Park

The extensive eastern boundary of Everglades National Park (ENP) in south Florida (USA) is subject to one of the most expensive and ambitious environmental restoration projects in history. Understanding and predicting the water quality interactions between the shallow aquifer and surface water is a key component in meeting current environmental regulations and fine-tuning ENP wetland restoration while still maintaining flood protection for the adjacent developed areas. Dynamic factor analysis (DFA), a recent technique for the study of multivariate non-stationary time-series, was applied to study fluctuations in groundwater quality in the area. More than two years of hydrological and water quality time series (rainfall; water table depth; and soil, ground and surface water concentrations of N-NO3-, N-NH4+, P-PO4(3-), Total P, F-and Cl-) from a small agricultural watershed adjacent to the ENP were selected for the study. The unexplained variability required for determining the concentration of each chemical in the 16 wells was greatly reduced by including in the analysis some of the observed time series as explanatory variables (rainfall, water table depth, and soil and canal water chemical concentration). DFA results showed that groundwater concentration of three of the agrochemical species studied (N-NO3-, P-PO4(3-)and Total P) were affected by the same explanatory variables (water table depth, enriched topsoil, and occurrence of a leaching rainfall event, in order of decreasing relative importance). This indicates that leaching by rainfall is the main mechanism explaining concentration peaks in groundwater. In the case of N-NH4+, in addition to leaching, groundwater concentration is governed by lateral exchange with canals. F-and Cl- are mainly affected by periods of dilution by rainfall recharge, and by exchange with the canals. The unstructured nature of the common trends found suggests that these are related to the complex spatially and temporally varying land use patterns in the watershed. The results indicate that peak concentrations of agrochemicals in groundwater could be reduced by improving fertilization practices (by splitting and modifying timing of applications) and by operating the regional canal system to maintain the water table low, especially during the rainy periods.     

Arsenic speciation and accumulation in evapoconcentrating waters of agricultural evaporation basins

To sustain agricultural productivity, evaporation basins (or ponds) have been widely used for the disposal of agricultural drainage in areas requiring subsurface drainage in the San Joaquin Valley of California, USA. The drainage water contains elevated concentration of trace elements including selenium (Se) and arsenic (As). Unlike Se, little information is available about As, a potentially high risk element. The objective of this study was to characterize the chemical behavior of As and acquire data for better understanding of biogeochemical processes and conditions affecting As fate in evaporation ponds. The study site was a 726 ha evaporation basin facility (containing 10 cells with water flowing in series) in the hydrologically closed Tulare Basin of California. We examined water chemistry, As concentration and speciation along the water flow path between cells as well as within the cells. Arsenic concentrations in the water increased linearly with Cl(-), a conservative ion from evapoconcentration. Reduced As species as arsenite [As(III)] and organic arsenic (org-As) also increased with increases in Cl(-) and salinity. Water samples with elevated EC (i.e., towards the end of flow path) had high dissolved organic matter, low dissolved oxygen, and elevated sulfide concentrations, indicating the development of reducing conditions. We hypothesize that such changes could facilitate the reduction of arsenate [As(V)] to As(III) and org-As. Elevated As in sediment profiles indicate a solid phase sink mechanism, but not significant enough to remove and reduce As concentrations in the water columns. These findings help us better define the processes that affect As in drainage facilities and contribute to our understanding of how As behaves in other regions of the world that have similar climatic and hydrogeochemical conditions.