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Field and laboratory arsenic speciation methods and their application to natural-water analysis

The toxic and carcinogenic properties of inorganic and organic arsenic species make their determination in natural water vitally important. Determination of individual inorganic and organic arsenic species is critical because the toxicology, mobility, and adsorptivity vary substantially. Several methods for the speciation of arsenic in groundwater, surface-water, and acid mine drainage sample matrices using field and laboratory techniques are presented. The methods provide quantitative determination of arsenite [As(III)], arsenate [As(V)], monomethylarsonate (MMA), dimethylarsinate (DMA), and roxarsone in 2-8min at detection limits of less than 1??g arsenic per liter (??g AsL-1). All the methods use anion exchange chromatography to separate the arsenic species and inductively coupled plasma-mass spectrometry as an arsenic-specific detector. Different methods were needed because some sample matrices did not have all arsenic species present or were incompatible with particular high-performance liquid chromatography (HPLC) mobile phases. The bias and variability of the methods were evaluated using total arsenic, As(III), As(V), DMA, and MMA results from more than 100 surface-water, groundwater, and acid mine drainage samples, and reference materials. Concentrations in test samples were as much as 13,000??g AsL-1 for As(III) and 3700??g AsL-1 for As(V). Methylated arsenic species were less than 100??g AsL-1 and were found only in certain surface-water samples, and roxarsone was not detected in any of the water samples tested. The distribution of inorganic arsenic species in the test samples ranged from 0% to 90% As(III). Laboratory-speciation method variability for As(III), As(V), MMA, and DMA in reagent water at 0.5??g AsL-1 was 8-13% (n=7). Field-speciation method variability for As(III) and As(V) at 1??g AsL-1 in reagent water was 3-4% (n=3). ?? 2003 Elsevier Ltd. All rights reserved.

Water Research↗

Small-scale, hydrogen-oxidizing-denitrifying bioreactor for treatment of nitrate-contaminated drinking water

Nitrate removal by hydrogen-coupled denitrification was examined using flow-through, packed-bed bioreactors to develop a small-scale, cost effective system for treating nitrate-contaminated drinking-water supplies. Nitrate removal was accomplished using a Rhodocyclus sp., strain HOD 5, isolated from a sole-source drinking-water aquifer. The autotrophic capacity of the purple non-sulfur photosynthetic bacterium made it particularly adept for this purpose. Initial tests used a commercial bioreactor filled with glass beads and countercurrent, non-sterile flow of an autotrophic, air-saturated, growth medium and hydrogen gas. Complete removal of 2 mM nitrate was achieved for more than 300 days of operation at a 2-h retention time. A low-cost hydrogen generator/bioreactor system was then constructed from readily available materials as a water treatment approach using the Rhodocyclus strain. After initial tests with the growth medium, the constructed system was tested using nitrate-amended drinking water obtained from fractured granite and sandstone aquifers, with moderate and low TDS loads, respectively. Incomplete nitrate removal was evident in both water types, with high-nitrite concentrations in the bioreactor output, due to a pH increase, which inhibited nitrite reduction. This was rectified by including carbon dioxide in the hydrogen stream. Additionally, complete nitrate removal was accomplished with wastewater-impacted surface water, with a concurrent decrease in dissolved organic carbon. The results of this study using three chemically distinct water supplies demonstrate that hydrogen-coupled denitrification can serve as the basis for small-scale remediation and that pilot-scale testing might be the next logical step.

Water Research↗

Nowcast modeling of Escherichia coli concentrations at multiple urban beaches of southern Lake Michigan

Predictive modeling for Escherichia coli concentrations at effluent-dominated beaches may be a favorable alternative to current, routinely criticized monitoring standards. The ability to model numerous beaches simultaneously and provide real-time data decreases cost and effort associated with beach monitoring. In 2004, five Lake Michigan beaches and the nearby Little Calumet River outfall were monitored for E. coli 7 days a week; on nine occasions, samples were analyzed for coliphage to indicate a sewage source. Ambient lake, river, and weather conditions were measured or obtained from independent monitoring sources. Positive tests for coliphage analysis indicated sewage was present in the river and on bathing beaches following heavy rainfall. Models were developed separately for days with prevailing onshore and offshore winds due to the strong influence of wind direction in determining the river's impact on the beaches. Using regression modeling, it was determined that during onshore winds, E. coli could be adequately predicted using wave height, lake chlorophyll and turbidity, and river turbidity ( R 2 =0.635 , N=94 ); model performance decreased for offshore winds using wave height, wave period, and precipitation ( R 2 =0.320 , N=124 ). Variation was better explained at individual beaches. Overall, the models only failed to predict E. coli levels above the EPA closure limit (235 CFU/100 ml) on five of eleven occasions, indicating that the model is a more reliable alternative to the monitoring approach employed at most recreational beaches.

Water Research↗

Sediment phosphate composition in relation to emergent macrophytes in the Doñana Marshes (SW Spain)

We have studied the effect of the presence of emergent macrophytes on the sediment phosphate composition of a eutrophic shallow marsh on the NE margin of Doñana (SW Spain). Top sediment and water samples were collected from both the open-water and the vegetated sites at three areas covered by different plant species: Scirpus maritimus , Juncus subulatus and Phragmites australis . The concentration of organic matter was significantly higher in the top sediment of sites covered by vegetation than in their adjacent open-water sites at the three vegetation areas. The P-fractional composition showed that the sediment was dominated by the inorganic P-fractions in all cases, reaching the highest concentration in the Ca-bound P-fraction (281–372 μg g −1 d.w.). The sum of all P-fractions was significantly higher in the top sediment of the sites covered by J. subulatus and S. maritimus than in their adjacent open-water sites, and so were the org-P fraction extracted by hot NaOH and the concentration of phytate within this fraction. Deposition of plant material on the top sediment of areas vegetated by J. subulatus and S. maritimus explains these differences. The P-fractional composition of the seeds from J. subulatus showed that they contained a large proportion of organic P-fractions, particularly of the fraction extracted by hot NaOH (1868 μg g −1 d.w., 85% of which was phytate). The presence of emergent macrophytes, therefore, influenced the distribution of P-fractions in the sediment depending on plant species. The P-bioavailability of shallow aquatic systems must be fully understood if wetlands are to be protected from further eutrophication.

Water Research↗

Effect of temperature, hydraulic residence time and elevated PCO2 on acid neutralization within a pulsed limestone bed reactor

Limestone has potential for reducing reagent costs and sludge volume associated with treatment of acid mine drainage, but its use is restricted by slow dissolution rates and the deposition of Fe, Al and Mn-based hydrolysis products on reactive surfaces. We evaluated a pulsed limestone bed (PLB) reactor (15 L/min capacity) that uses a CO2 pretreatment step to accelerate dissolution and hydraulic shearing forces provided by intermittent fluidization to abrade and carry away surface scales. We established the effects of hydraulic residence time (HRT, 5.1-15.9 min), temperature (T, 12-22 ??C) and CO2 tension (PCO2, 34.5-206.8 kPa) on effluent quality when inlet acidity (Acy) was fixed at 440 mg/L (pH=2.48) with H2SO4. The PLB reactor neutralized all H+ acidity (N=80) while concurrently providing unusually high levels of effluent alkalinity (247-1028 mg/L as CaCO3) that allow for side-stream treatment with blending. Alkalinity (Alk) yields rose with increases in PCO2, HRT and settled bed height (BH, cm) and decreased with T following the relationship (R2=0.926; p<0.001): (Alk)non-filtered=-548.726+33.571??(PCO2)0.5+33.671??(HRT)+7.734??(BH)-5.197??(T). Numerical modeling showed CO2 feed requirements for a target Alk yield decrease with increases in HRT, T and the efficiency of off-gas (CO2) recycling. ?? 2007 Elsevier Ltd. All rights reserved.

Water Research↗

Population structure of Cladophora -borne Escherichia coli in nearshore water of Lake Michigan

We previously reported that the macrophytic green alga Cladophora harbors high densities (up to 10 6 colony-forming units/g dry weight) of the fecal indicator bacteria, Escherichia coli and enterococci, in shoreline waters of Lake Michigan. However, the population structure and genetic relatedness of Cladophora -borne indicator bacteria remain poorly understood. In this study, 835 E. coli isolates were collected from Cladophora tufts (mats) growing on rocks from a breakwater located within the Indiana Dunes National Lakeshore in northwest Indiana. The horizontal fluorophore enhanced rep-PCR (HFERP) DNA fingerprinting technique was used to determine the genetic relatedness of the isolates to each other and to those in a library of E. coli DNA fingerprints. While the E. coli isolates from Cladophora showed a high degree of genetic relatedness (⩾92% similarity), in most cases, however, the isolates were genetically distinct. The Shannon diversity index for the population was very high (5.39). Both spatial and temporal influences contributed to the genetic diversity. There was a strong association of isolate genotypes by location (79% and 80% for lake- and ditch-side samplings, respectively), and isolates collected from 2002 were distinctly different from those obtained in 2003. Cladophora -borne E. coli isolates represented a unique group, which was distinct from other E. coli isolates in the DNA fingerprint library tested. Taken together, these results indicate that E. coli strains associated with Cladophora may be a recurring source of indicator bacteria to the nearshore beach.

Water Research↗

Fecal indicator bacteria and Salmonella in ponds managed as bird habitat, San Francisco Bay, California, USA

Throughout the world, coastal resource managers are encouraging the restoration of previously modified coastal habitats back into wetlands and managed ponds for their ecosystem value. Because many coastal wetlands are adjacent to urban centers and waters used for human recreation, it is important to understand how wildlife can affect water quality. We measured fecal indicator bacteria (FIB) concentrations, presence/absence of Salmonella, bird abundance, and physico-chemical parameters in two coastal, managed ponds and adjacent sloughs for 4 weeks during the summer and winter in 2006. We characterized the microbial water quality in these waters relative to state water-quality standards and examined the relationship between FIB, bird abundance, and physico-chemical parameters. A box model approach was utilized to determine the net source or sink of FIB in the ponds during the study periods. FIB concentrations often exceeded state standards, particularly in the summer, and microbial water quality in the sloughs was generally lower than in ponds during both seasons. Specifically, the inflow of water from the sloughs to the ponds during the summer, more so than waterfowl use, appeared to increase the FIB concentrations in the ponds. The box model results suggested that the ponds served as net wetland sources and sinks for FIB, and high bird abundances in the winter likely contributed to net winter source terms for two of the three FIB in both ponds. Eight serovars of the human pathogen Salmonella were isolated from slough and pond waters, although the source of the pathogen to these wetlands was not identified. Thus, it appeared that factors other than bird abundance were most important in modulating FIB concentrations in these ponds.

Water Research↗

Seasonal stability of Cladophora-associated Salmonella in Lake Michigan watersheds

The bacterial pathogens Shigella, Salmonella, Campylobacter, and shiga toxin-producing E. coli (STEC) were recently found to be associated with Cladophora growing in southern Lake Michigan. Preliminary results indicated that the Salmonella strains associated with Cladophora were genetically identical to each other. However, because of the small sample size (n = 37 isolates) and a lack of information on spatial-temporal relationships, the nature of the association between Cladophora and Salmonella remained speculative. In this study, we investigated the population structure and genetic relatedness of a large number of Cladophora-borne Salmonella isolates from Lake Michigan (n = 133), as well as those isolated from stream and lake water (n = 31), aquatic plants (n = 8), and beach sands and sediments (n = 8) from adjacent watersheds. Salmonella isolates were collected during 2005-2007 between May and August from Lake Michigan beachsheds in Wisconsin, Illinois, and Indiana. The genetic relatedness of Salmonella isolates was examined by using the horizontal, fluorophore-enhanced rep-PCR (HFERP) DNA fingerprinting technique. While the Salmonella isolates associated with Cladophora exhibited a high degree of genetic relatedness (???92% similarity), the isolates were not all genetically identical. Spatial and temporal relationships were evident in the populations examined, with tight clustering of the isolates both by year and location. These findings suggest that the relationship between Salmonella and Cladophora is likely casual and is related to input sources (e.g. wastewater, runoff, birds) and the predominant Salmonella genotype surviving in the environment during a given season. Our studies indicate that Cladophora is likely an important reservoir for Salmonella and other enteric bacterial pathogens in Lake Michigan beachsheds, which in turn may influence nearshore water quality. ?? 2008 Elsevier Ltd.

Water Research↗

Removal of phosphorus from agricultural wastewaters using adsorption media prepared from acid mine drainage sludge

Excess phosphorus in wastewaters promotes eutrophication in receiving waterways. A??cost-effective method for the removal of phosphorus from water would significantly reduce the impact of such wastewaters on the environment. Acid mine drainage sludge is a waste product produced by the neutralization of acid mine drainage, and consists mainly of the same metal hydroxides used in traditional wastewater treatment for the removal of phosphorus. In this paper, we describe a method for the drying and pelletization of acid mine drainage sludge that results in a particulate media, which we have termed Ferroxysorb, for the removal of phosphorus from wastewater in an efficient packed bed contactor. Adsorption capacities are high, and kinetics rapid, such that a contact time of less than 5 min is sufficient for removal of 60-90% of the phosphorus, depending on the feed concentration and time in service. In addition, the adsorption capacity of the Ferroxysorb media was increased dramatically by using two columns in an alternating sequence so that each sludge bed receives alternating rest and adsorption cycles. A stripping procedure based on treatment with dilute sodium hydroxide was also developed that allows for recovery of the P from the media, with the possibility of generating a marketable fertilizer product. These results indicate that acid mine drainage sludges - hitherto thought of as undesirable wastes - can be used to remove phosphorus from wastewater, thus offsetting a portion of acid mine drainage treatment costs while at the same time improving water quality in sensitive watersheds.

Water Research↗

Evaluation of two spike-and-recovery controls for assessment of extraction efficiency in microbial source tracking studies

Quantitative PCR (qPCR), applied to complex environmental samples such as water, wastewater, and feces, is susceptible to methodological and sample related biases. In this study, we evaluated two exogenous DNA spike-and-recovery controls as proxies for recovery efficiency of Bacteroidales 16S rDNA gene sequences (AllBac and qHF183) that are used for microbial source tracking (MST) in river water. Two controls-(1) the plant pathogen Pantoea stewartii, carrying the chromosomal target gene cpsD, and (2) Escherichia coli, carrying the plasmid-borne target gene DsRed2-were added to raw water samples immediately prior to concentration and DNA extraction for qPCR. When applied to samples processed in replicate, recovery of each control was positively correlated with the observed concentration of each MST marker. Adjustment of MST marker concentrations according to recovery efficiency reduced variability in replicate analyses when consistent processing and extraction methodologies were applied. Although the effects of this procedure on accuracy could not be tested due to uncertainties in control DNA concentrations, the observed reduction in variability should improve the strength of statistical comparisons. These findings suggest that either of the tested spike-and-recovery controls can be useful to measure efficiency of extraction and recovery in routine laboratory processing. ?? 2009 Elsevier Ltd.

Water Research↗

Comparison of immunomagnetic separation/adenosine triphosphate rapid method to traditional culture-based method for E. coli and enterococci enumeration in wastewater

Untreated wastewater samples from California, North Carolina, and Ohio were analyzed by the immunomagnetic separation/adenosine triphosphate (IMS/ATP) method and the traditional culture-based method for E. coli and enterococci concentrations. The IMS/ATP method concentrates target bacteria by immunomagnetic separation and then quantifies captured bacteria by measuring bioluminescence induced by release of ATP from the bacterial cells. Results from this method are available within 1 h from the start of sample processing. Significant linear correlations were found between the IMS/ATP results and results from traditional culture-based methods for E. coli and enterococci enumeration for one location in California, two locations in North Carolina, and one location in Ohio (r??values ranged from 0.87 to 0.97). No significant linear relation was found for a second location in California that treats a complex mixture of residential and industrial wastewater. With the exception of one location, IMS/ATP showed promise as a rapid method for the quantification of faecal-indicator organisms in wastewater.

Water Research↗

Effects of altered groundwater chemistry upon the pH-dependency and magnitude of bacterial attachment during transport within an organically contaminated sandy aquifer

The effects of a dilute (ionic strength = 5 × 10 −3 M) plume of treated sewage, with elevated levels (3.9 mg/L) of dissolved organic carbon (DOC), upon the pH-dependency and magnitude of bacterial transport through an iron-laden, quartz sand aquifer (Cape Cod, MA) were evaluated using sets of replicate, static minicolumns. Compared with uncontaminated groundwater, the plume chemistry diminished bacterial attachment under mildly acidic (pH 5.0–6.5) in-situ conditions, in spite of the 5-fold increase in ionic strength and substantively enhanced attachment under more alkaline conditions. The effects of the hydrophobic neutral and total fractions of the plume DOC; modest concentrations of fulvic and humic acids (1.5 mg/L); linear alkyl benzene sulfonate (LAS) (25 mg/L); Imbentin (200 μg/L), a model nonionic surfactant; sulfate (28 mg/L); and calcium (20 mg/L) varied sharply in response to relatively small changes in pH, although the plume constituents collectively decreased the pH-dependency of bacterial attachment. LAS and other hydrophobic neutrals (collectively representing only ∼3% of the plume DOC) had a disproportionately large effect upon bacterial attachment, as did the elevated concentrations of sulfate within the plume. The findings further suggest that the roles of organic plume constituents in transport or bacteria through acidic aquifer sediments can be very different than would be predicted from column studies performed at circumneutral pH and that the inorganic constituents within the plume cannot be ignored.

Water Research↗

Influence of organic matter on the transport of Cryptosporidium parvum oocysts in a ferric oxyhydroxide-coated quartz sand saturated porous medium

To assess the effect of organic matter on the transport of Cryptosporidium parvum oocysts in a geochemically heterogeneous saturated porous medium, we measured the breakthrough and collision efficiencies of oocysts as a function of dissolved organic matter concentration in a flow-through column containing ferric oxyhydroxide-coated sand. We characterized the surface properties of the oocysts and ferric oxyhydroxide-coated sand using microelectrophoresis and streaming potential, respectively, and the amount of organic matter adsorbed on the ferric oxyhydroxide-coated sand as a function of the concentration of dissolved organic matter (a fulvic acid isolated from Florida Everglades water). The dissolved organic matter had no significant effect on the zeta potential of the oocysts. Low concentrations of dissolved organic matter were responsible for reversing the charge of the ferric oxyhydroxide-coated sand surface from positive to negative. The charge reversal and accumulation of negative charge on the ferric oxyhydroxide-coated sand led to increases in oocyst breakthrough and decreases in oocyst collision efficiency with increasing dissolved organic matter concentration. The increase in dissolved organic matter concentration from 0 to 20 mg L -1 resulted in a two-fold decrease in the collision efficiency.

Water Research↗

Influence of organic carbon loading, sediment associated metal oxide content and sediment grain size distributions upon Cryptosporidium parvum removal during riverbank filtration operations, Sonoma County, CA

This study assessed the efficacy for removing Cryptosporidium parvum oocysts of poorly sorted, Fe- and Al-rich, subsurface sediments collected from 0.9 to 4.9 and 1.7–13.9 m below land surface at an operating riverbank filtration (RBF) site (Russian River, Sonoma County, CA). Both formaldehyde-killed oocysts and oocyst-sized (3 μm) microspheres were employed in sediment-packed flow-through and static columns. The degree of surface coverage of metal oxides on sediment grain surfaces correlated strongly with the degrees of oocyst and microsphere removals. In contrast, average grain size ( D 50 ) was not a good indicator of either microsphere or oocyst removal, suggesting that the primary mechanism of immobilization within these sediments is sorptive filtration rather than physical straining. A low specific UV absorbance (SUVA) for organic matter isolated from the Russian River, suggested that the modest concentration of the SUVA component (0.8 mg L −1 ) of the 2.2 mg L −1 dissolved organic carbon (DOC) is relatively unreactive. Nevertheless, an amendment of 2.2 mg L −1 of isolated river DOC to column sediments resulted in up to a 35.7% decrease in sorption of oocysts and (or) oocyst-sized microspheres. Amendments (3.2 μM) of the anionic surfactant, sodium dodecyl benzene sulfonate (SDBS) also caused substantive decreases (up to 31.9 times) in colloid filtration. Although the grain-surface metal oxides were found to have a high colloid-removal capacity, our study suggested that any major changes within the watershed that would result in long-term alterations in either the quantity and (or) the character of the river's DOC could alter the effectiveness of pathogen removal during RBF operations.

Water Research↗

Pathways for arsenic from sediments to groundwater to streams: Biogeochemical processes in the Inner Coastal Plain, New Jersey, USA

The Cretaceous and Tertiary sediments that underlie the Inner Coastal Plain of New Jersey contain the arsenic-rich mineral glauconite. Streambed sediments in two Inner Coastal Plain streams (Crosswicks and Raccoon Creeks) that traverse these glauconitic deposits are enriched in arsenic (15–25 mg/kg), and groundwater discharging to the streams contains elevated levels of arsenic (>80 μg/L at a site on Crosswicks Creek) with arsenite generally the dominant species. Low dissolved oxygen, low or undetectable levels of nitrate and sulfate, detectable sulfide concentrations, and high concentrations of iron and dissolved organic carbon (DOC) in the groundwater indicate that reducing environments are present beneath the streambeds and that microbial activity, fueled by the DOC, is involved in releasing arsenic and iron from the geologic materials. In groundwater with the highest arsenic concentrations at Crosswicks Creek, arsenic respiratory reductase gene ( arrA ) indicated the presence of arsenic-reducing microbes. From extracted DNA, 16s rRNA gene sequences indicate the microbial community may include arsenic-reducing bacteria that have not yet been described. Once in the stream, iron is oxidized and precipitates as hydroxide coatings on the sediments. Arsenite also is oxidized and co-precipitates with or is sorbed to the iron hydroxides. Consequently, dissolved arsenic concentrations are lower in streamwater than in the groundwater, but the arsenic contributed by groundwater becomes part of the arsenic load in the stream when sediments are suspended during high flow. A strong positive relation between concentrations of arsenic and DOC in the groundwater samples indicates that any process—natural or anthropogenic—that increases the organic carbon concentration in the groundwater could stimulate microbial activity and thus increase the amount of arsenic that is released from the geologic materials.

New Jersey↗

Comparison of transport and attachment behaviors of Cryptosporidium parvum oocysts and oocyst-sized microspheres being advected through three minerologically different granular porous media

In order to gain more information about the fate of Cryptosporidium parvum oocysts in tropical volcanic soils, the transport and attachment behaviors of oocysts and oocyst-sized polystyrene microspheres were studied in the presence of two soils. These soils were chosen because of their differing chemical and physical properties, i.e., an organic-rich (43–46% by mass) volcanic ash-derived soil from the island of Hawaii, and a red, iron (22–29% by mass), aluminum (29–45% by mass), and clay-rich (68–76% by mass) volcanic soil from the island of Oahu. A third agricultural soil, an organic- (13% by mass) and quartz-rich (40% by mass) soil from Illinois, was included for reference. In 10-cm long flow-through columns, oocysts and microspheres advecting through the red volcanic soil were almost completely (98% and 99%) immobilized. The modest breakthrough resulted from preferential flow-path structure inadvertently created by soil-particle aggregation during the re-wetting process. Although a high (99%) removal of oocysts and microsphere within the volcanic ash soil occurred initially, further examination revealed that transport was merely retarded because of highly reversible interactions with grain surfaces. Judging from the slope of the substantive and protracted tail of the breakthrough curve for the 1.8-μm microspheres, almost all (>99%) predictably would be recovered within ∼4000 pore volumes. This suggests that once contaminated, the volcanic ash soil could serve as a reservoir for subsequent contamination of groundwater, at least for pathogens of similar size or smaller. Because of the highly reversible nature of organic colloid immobilization in this soil type, C. parvum could contaminate surface water should overland flow during heavy precipitation events pick up near-surface grains to which they are attached. Surprisingly, oocyst and microsphere attachment to the reference soil from Illinois appeared to be at least as sensitive to changes in pH as was observed for the red, metal-oxide rich soil from Oahu. In contrast, colloidal attachment in the organic-rich, volcanic ash soil was relatively insensitive to changes in pH in spite of the high iron content. Given the fundamental differences in transport behavior of oocyst-sized colloids within the two volcanic soils of similar origin, agricultural practices modified to lessen C. parvum contamination of ground or surface water would necessitate taking the individual soil properties into account.

Water Research↗

Multi-scale temporal and spatial variation in genotypic composition of Cladophora-borne Escherichia coli populations in Lake Michigan

High concentrations of Escherichia coli in mats of Cladophora in the Great Lakes have raised concern over the continued use of this bacterium as an indicator of microbial water quality. Determining the impacts of these environmentally abundant E. coli, however, necessitates a better understanding of their ecology. In this study, the population structure of 4285 Cladophora-borne E. coli isolates, obtained over multiple three day periods from Lake Michigan Cladophora mats in 2007-2009, was examined by using DNA fingerprint analyses. In contrast to previous studies that have been done using isolates from attached Cladophora obtained over large time scales and distances, the extensive sampling done here on free-floating mats over successive days at multiple sites provided a large dataset that allowed for a detailed examination of changes in population structure over a wide range of spatial and temporal scales. While Cladophora-borne E. coli populations were highly diverse and consisted of many unique isolates, multiple clonal groups were also present and accounted for approximately 33% of all isolates examined. Patterns in population structure were also evident. At the broadest scales, E. coli populations showed some temporal clustering when examined by year, but did not show good spatial distinction among sites. E. coli population structure also showed significant patterns at much finer temporal scales. Populations were distinct on an individual mat basis at a given site, and on individual days within a single mat. Results of these studies indicate that Cladophora-borne E. coli populations consist of a mixture of stable, and possibly naturalized, strains that persist during the life of the mat, and more unique, transient strains that can change over rapid time scales. It is clear that further study of microbial processes at fine spatial and temporal scales is needed, and that caution must be taken when interpolating short term microbial dynamics from results obtained from weekly or monthly samples.

Water Research↗

FeS-coated sand for removal of arsenic(III) under anaerobic conditions in permeable reactive barriers

Iron sulfide (as mackinawite, FeS) has shown considerable promise as a material for the removal of As(III) under anoxic conditions. However, as a nanoparticulate material, synthetic FeS is not suitable for use in conventional permeable reactive barriers (PRBs). This study developed a methodology for coating a natural silica sand to produce a material of an appropriate diameter for a PRB. Aging time, pH, rinse time, and volume ratios were varied, with a maximum coating of 4.0 mg FeS/g sand achieved using a pH 5.5 solution at a 1:4 volume ratio (sand: 2 g/L FeS suspension), three days of aging and no rinsing. Comparing the mass deposited on the sand, which had a natural iron-oxide coating, with and without chemical washing showed that the iron-oxide coating was essential to the formation of a stable FeS coating. Scanning electron microscopy images of the FeS-coated sand showed a patchwise FeS surface coating. X-ray photoelectron spectroscopy showed a partial oxidation of the Fe(II) to Fe(III) during the coating process, and some oxidation of S to polysulfides. Removal of As(III) by FeS-coated sand was 30% of that by nanoparticulate FeS at pH 5 and 7. At pH 9, the relative removal was 400%, perhaps due to the natural oxide coating of the sand or a secondary mineral phase from mackinawite oxidation. Although many studies have investigated the coating of sands with iron oxides, little prior work reports coating with iron sulfides. The results suggest that a suitable PRB material for the removal of As(III) under anoxic conditions can be produced through the deposition of a coating of FeS onto natural silica sand with an iron-oxide coating. Iron sulfide (as mackinawite, FeS) has shown considerable promise as a material for the removal of As(III) under anoxic conditions. However, as a nanoparticulate material, synthetic FeS is not suitable for use in conventional permeable reactive barriers (PRBs). This study developed a methodology for coating a natural silica sand to produce a material of an appropriate diameter for a PRB. Aging time, pH, rinse time, and volume ratios were varied, with a maximum coating of 4.0 mg FeS/g sand achieved using a pH 5.5 solution at a 1:4 volume ratio (sand: 2 g/L FeS suspension), three days of aging and no rinsing. Comparing the mass deposited on the sand, which had a natural iron-oxide coating, with and without chemical washing showed that the iron-oxide coating was essential to the formation of a stable FeS coating. Scanning electron microscopy images of the FeS-coated sand showed a patchwise FeS surface coating. X-ray photoelectron spectroscopy showed a partial oxidation of the Fe(II) to Fe(III) during the coating process, and some oxidation of S to polysulfides. Removal of As(III) by FeS-coated sand was 30% of that by nanoparticulate FeS at pH 5 and 7. At pH 9, the relative removal was 400%, perhaps due to the natural oxide coating of the sand or a secondary mineral phase from mackinawite oxidation. Although many studies have investigated the coating of sands with iron oxides, little prior work reports coating with iron sulfides. The results suggest that a suitable PRB material for the removal of As(III) under anoxic conditions can be produced through the deposition of a coating of FeS onto natural silica sand with an iron-oxide coating.

Water Research↗