Passive in situ remediation of metal-polluted water with caustic magnesia: evidence from column experiments

Passive remediation consists of a permeable system that enables the water to pass through while retaining metals by means of biogeochemical reactions. Conventional passive treatments are based on calcite dissolution. This increases the pH to values between 6 and 7, which are insufficiently high to precipitate divalent metals. Alternative treatments are based on sulfate reduction with organic matter in order to precipitate metal sulfides. However, redox reactions are usually too slow to treat large groundwater flows as currently found in gravel aquifers (>50 m/a). Caustic magnesia obtained from calcination of magnesium carbonate was tested as an alternative material to devising passive remediation systems. Caustic magnesia reacts with water to form magnesium hydroxide, which dissolves, increasing the pH to values higher than 8.5. Then zinc and lead are mainly precipitated as hydroxides, copper is precipitated as hydroxysulfate, and manganese(II) is oxidized and precipitated as manganese(III) oxides. Thus, metal concentrations as high as 75 mg/L in the inflowing water are depleted to values below 0.04 mg/L. Magnesia dissolution is sufficiently fast to treat flows as high as 100 m/a. The new precipitates may lead to a permeability drop in the porous treating system. Mixtures of caustic magnesia and an inert material such as silica sand (approximately 50% of each) have been shown to be as reactive as pure magnesia and permeable for a longer time (more than 10 months and 1000 pore vol).     

Uptake of dissolved Ag,Cd, and Co by the clam,Macoma balthica: relative importance of overlying water,oxic pore water,and burrow water

The facultative deposit-feeding clam Macoma balthica is used as a bioindicator organism for assessing coastal metal contamination. Previous work has evaluated the assimilation of metals from different possible food sources for this clam, but no studies have measured the uptake rates of metals from different dissolved sources. This study specifically compares three different dissolved sources: overlying water (SW), oxic pore water (OPW) from a depth of <1 cm (entrained during surface deposit feeding), and burrow water (BW) (a mixture of anoxic pore water and overlying water). Uptake rates of dissolved Ag, Cd, and Co in M. balthica were measured in short-term laboratory experiments using radiotracers. Clams were exposed to metals in water only for SW and surface OPW treatments. In the BW treatment, metal uptake was compared in clams placed in radiolabeled organic-poor or organic-rich sediment under conditions in which feeding was inhibited. Uptake rate constantsfrom SW for Ag, Cd, and Co were 0.35, 0.033, and 0.035 L g(-1) day(-1), respectively. Lower uptake of dissolved metals from OPW was noted but was only significant for Co. Metal uptake from BW and SW were also comparable; however, the trend showed lower Ag and higher Co uptake from BW. Metal distributions and concentrations in the two radiolabeled sediments were affected by active irrigation of SW into the burrows; dissolved metal concentrations in BW were approximately 30% lower than that in the bulk pore water concentrations. In the organic-rich sediment, Cd and Ag partitioned more in the dissolved phase (<0.2 microm) and Co more in the particulate phase as compared with the organic-poor sediment. A sensitivity analysis using measured rate constants for uptake and a range of metal concentrations from field studies suggested that, under most conditions, uptake of dissolved Ag is primarily from OPW, Co is mostly from BW, and Cd uptake varies depending on its concentration in each compartment. Little Co or Ag is likely to be taken up from SW, whereas 20-50% of Cd may be accumulated from this source. Thus, SW, OPW, and BW are all potential sources of metals for M. balthica, and the relative importance of these sources differs among metals and is dependent on the dissolved metal concentrations in each compartment.     

Measurement of heavy metal speciation over redox gradients in natural water-sediment interfaces and implications for uptake by benthic organisms

The sediment or fauna incubation experiment (SOFIE) is an experimental research tool that was developed to analyze concentrations and chemical speciation of heavy metals in pore waters of natural, undisturbed sediments or water-sediment interfaces over time, while simultaneously conducting exposure tests with sediment-dwelling organisms. In this way, concentrations of chemical species are directly linked to accumulation by biota. It is shown that discrete gradients of redox-sensitive metals and nutrients occur over very small intervals. These gradients differ from those of free metal ion activities. Speciation affects the uptake of metals by sediment-dwelling organisms, which, in their turn, have a significant effect on metal speciation. With reaction kinetics that differ per metal, uptake of metals by organisms from the water phase may be hindered (e.g., Cu, Zn) or promoted (e.g., Ni, As). Time-varying exposure concentrations of metals were incorporated in uptake and elimination models. Body concentrations of Cd, Cu, Ni, and Zn in the aquatic oligochaete Limnodrilus could best be described by the time-varying free ion concentration in the overlying water. Body concentrations of As and Pb were best described by sediment pore water concentrations. It is concluded that SOFIE provides the necessary experimental tool to support, in a mechanistic way, environmental risk assessments of contaminants.     

Comparison of five methods for measuring sediment toxicity of hydrophobic contaminants

Sediment toxicity from hydrophobic organic compounds (HOCs) is complicated by chemical partitioning among multiple phases and sediment-specific bioavailability. In this study, we used three hydrophobic pyrethroid insecticides as test compounds and derived 10-d median lethal concentrations (LC50s) for Chironomus tentans in three different sediments. The LC50s were expressed using HOC concentrations on a bulk sediment basis (C(S)), organic carbon (OC)-normalized sediment basis (C(S-OC)), porewater basis (C(PW)), dissolved organic carbon (DOC)-normalized porewater basis (C(PW-DOC)), and freely dissolved porewater basis (C(free)). The bulk phase C(S) and C(PW) yielded highly variable LC50s across sediment types, whereas the use of normalized concentrations C(S-OC) and C(PW-DOC) generally reduced variability due to sediment type but not that due to aging. In contrast, LC50s based on C(free) were essentially independent of sediment conditions. The sediment pore water samples contained approximately 20-90 mg L(-1) DOC, and the C(free) expressed as a percentage of the total bulk pore water concentration ranged from 9 to 28% for fenpropathrin (mean = 19%), 8 to 18% for bifenthrin (mean = 13%), and 3 to 8% for cyfluthrin (mean = 6%) across the different sediments. These results indicate thatthe use of C(free) reduces uncertainties caused by sediment variables such as OC properties and aging effects.     

Sediment toxicity of a rapidly biodegrading nonionic surfactant: Comparing the equilibrium partitioning approach with measurements in pore water

The equilibrium partitioning theory (EqP) assumes that the toxicity of nonionic surfactants in sediment can be predicted from water-only toxicity data as long as the effect concentrations are properly normalized for chemical activity. Therefore, in marine sediment toxicity tests with the model alcohol ethoxylate (AE), C12EO8, freely dissolved concentrations were both measured via solid-phase microextraction and predicted using sorption coefficients. In fully equilibrated test systems (including the overlying water), both methods showed that concentrations in the pore water of the spiked sediment layer causing 50% mortality (LC50) to the amphipod Corophium volutator were in the same range as LC50 values for amphipods exposed to AE in seawater only. In the sediment systems, AE concentrations in the pore water remained constant up to 15 days, while concentrations in the water overlying the sediment decreased to less than 1% of initial concentrations within 6 days due to biodegradation. In such disequilibrated test systems, C. volutator survived pore water dissolved concentrations that were above the LC50. Apparently, this burrowing amphipod is able to exploit the low chemical activity in the overlying water as a refuge from sediment exposure.     

Advection dominated transport of polycyclic aromatic hydrocarbons in amended sediment caps

Typical sand caps used for sediment remediation have little sorption capacity to retard the migration of hydrophobic contaminants such as PAHs that can be mobilized by significant groundwater flow. Laboratory column experiments were performed using contaminated sediments and capping materials from a creosote contaminated USEPA Superfund site. Azoic laboratory column experiments demonstrated rapid breakthrough of lower molecular weight PAHs when groundwater seepage was simulated through a column packed with coarse sand capping material. After eight pore volumes of flow, most PAHs measured showed at least 50% of initial source pore water concentrations at the surface of 65 cm capping material. PAH concentration in the cap solids was low and comparable to background levels typically seen in urban depositional sediment, but the pore water concentrations were high. Column experiments with a peat amendment delayed PAH breakthrough. The most dramatic result was observed for caps amended with activated carbon at a dose of 2% by dry weight. PAH concentrations in the pore water of the activated carbon amended caps were 3-4 orders of magnitude lower (0.04 ± 0.02 μg/L for pyrene) than concentrations in the pore water of the source sediments (26.2 ± 5.6 μg/L for pyrene) even after several hundred pore volumes of flow. Enhancing the sorption capacity of caps with activated carbon amendment even at a lower dose of 0.2% demonstrated a significant impact on contaminant retardation suggesting consideration of active capping for field sites prone to groundwater upwelling or where thin caps are desired to minimize change in bathymetry and impacts to aquatic habitats.     

Sub-lethal effects of copper to benthic invertebrates explained by sediment properties and dietary exposure

The next generation of sediment quality guidelines (SQGs) requires better established causal links between the chronic exposure and effects of metals from both dissolved and dietary sources. The potential for dietary exposure from sediment metals to cause toxic effects to benthic invertebrates is strongly influenced by the metal-binding properties of the sediments. For relatively oxidized sediments, sublethal effects of copper to the epibenthic deposit-feeding amphipod, Melita plumulosa, and the benthic harpacticoid copepod, Nitocra spinipes, were investigated. Effects on reproduction were strongly influenced by the properties of the sediments and sediment-bound copper was found to be the major contribution to the toxicity. For sediments with the same total copper concentrations, effects were less for sediments with greater concentrations of fine particles (<63 μm sediment) or particulate organic carbon (OC). The OC-normalized copper concentration in the <63 μm sediment fraction provided a single effects threshold for all sediment types. For M. plumulosa and N. spinipes, the 10% effect concentrations (EC10s) were 5.2 and 4.8 mg <63 μm Cu g(-1) OC. These chronic EC10s indicate that a SQG of 3.5 mg <63 μm Cu g(-1) OC, that was previously proposed based on a species sensitivity distribution of acute no effects thresholds data for 12 benthic organisms, will be protective for these species. The study confirms the appropriateness of using SQGs that vary with sediment properties and that SQGs of this form provide adequate protection for metal exposure via both dissolved and dietary exposure pathways.     

Quantitative 3-D elemental mapping by LA-ICP-MS of a basaltic clast from the Hanford 300 Area, Washington, USA

Laser ablation with inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to measure elemental concentrations at the 100-μm scale in a 3-dimensional manner within a basaltic clast sample collected from the Hanford 300 Area in south-central Washington State, United States. A calibration method was developed to quantify the LA-ICP-MS signal response using a constant-sum mass fraction of eight major elements; the method produced reasonable concentration measurements for both major and trace elements when compared to a standard basalt sample with known concentrations. 3-Dimensional maps (stacked 2-D contour layers, each representing 2100 μm × 2100 μm) show relatively uniform concentration with depth for intrinsic elements such as Si, Na, and Sr. However, U and Cu accumulation were observed near the sample surface, consistent with the site's release history of these contaminants. U and Cu show substantial heterogeneity in their concentration distributions within horizontal slices, while the intrinsic elements are essentially uniformly distributed. From these measured U concentrations and published grain size distributions, gravel and cobbles were estimated to contain about 1% of the contaminant U, implicating the coarse fraction as a long-term release source.     

Simultaneous release of metals and sulfide in lacustrine sediment

A single DGT (diffusive gradient in thin films) probe that could measure metals and sulfide simultaneously and at the same location was deployed in the surface sediment of a productive lake (Esthwaite Water). It contained a layer of AgI that binds sulfide overlying a layer of chelating resin that binds metals. Analysis for sulfide in two dimensions showed local sources of sulfide, 1-5 mm in diameter, at 8-11 cm depth within the sediment. A transect of trace metals measured at 100-microm intervals through the largest sulfide "hot spot" demonstrated concomitant release of Fe, Mn, Cu, Ni, and Co. Substantial supersaturation with respect to metal sulfides was observed for Fe and Co at the site of metal generation, but at a distance of less than 1 mm, solution concentrations were consistent with equilibration with amorphous FeS and CoS phases. Simple mass balance calculations were consistent with Fe being supplied from reductive dissolution of its oxides and with sulfide being supplied from reduction of sulfate. The observed concentrations of Cu, Ni, Co, and Mn could be accounted for by their release from iron oxides without invoking Mn reduction. The metals are removed rapidly (approximately 1 min) at the edge of the hot spot. These first observations of the simultaneous release of trace metals and sulfide are consistent with the known removal of metals by formation of their insoluble sulfides if the in situ kinetics of metal sulfide formation is on this time scale. The coproduction of reduced Fe and S suggests that iron- and sulfate-reducing bacteria may exist together in the same localized zone of actively decomposing organic matter.     

Chemical speciation of Zn,Cd, Cu,and Pb in pore waters of agricultural and contaminated soils using Donnan dialysis

Knowledge of trace metal speciation in soil pore waters is important in addressing metal bioavailability and risk assessment of contaminated soils. Numerous analytical methods have been utilized for determining trace metal speciation in aqueous environmental matrixes; however, most of these methods suffer from significant interferences. The Donnan dialysis membrane technique minimizes these interferences and has been used in this study to determine free Zn2+, Cd2+, Cu2+, and Pb2+ activities in pore waters from 15 agricultural and 12 long-term contaminated soils. The soils vary widely in their origin, pH, organic carbon content, and total metal concentrations. Pore water pM2+ activities also covered a wide range and were controlled by soil pH and total metal concentrations. For the agricultural soils, most of the free metal activities were below detection limit, apart from Zn2+ for which the fraction of free Zn2+ in soluble Zn ranged from 2.3 to 87% (mean 43%). Five of the agricultural soils had detectable free Cd2+ with fractions of free metal ranging from 59 to 102% (mean 75%). For the contaminated soils with detectable free metal concentrations, the fraction of free metal as a percentage of soluble metal varied from 9.9 to 97% (mean 50%) for Zn2+, from 22 to 86% (mean 49%) for Cd2+, from 0.4 to 32.1% (mean 5%) for Cu2+, and from 2.9 to 48.8% (mean 20.1%) for Pb2+. For the contaminated soils, the equilibrium speciation programs GEOCHEM and WHAM Model VI provided reasonable estimates of free Zn2+ fractions in comparison to the measured fractions (R2 approximately 0.7), while estimates of free Cd2+ fractions were less agreeable (R2 approximately 0.5). The models generally predicted stronger binding of Cu2+ to DOC and hence lower fractions of free Cu2+ as compared with the observed fractions. The binding of Cu2+ and Pb2+ to DOC predicted by WHAM Model VI was much strongerthan that predicted by GEOCHEM.     

Dynamic model for the accumulation of cadmium and zinc from water and sediment by the aquatic oligochaete, Tubifex tubifex

In aquatic environments, organisms are exposed to and accumulate metals via waterborne and dietary routes including ingested sediment. A key element in understanding metal uptake and accumulation is information concerning the relative importance of the routes of uptake and the kinetics of the processes. In this work the bioaccumulation of the essential element zinc and the nonessential element cadmium were studied from the aqueous and sediment phase, in the cosmopolitan oligochaete Tubifex tubifex, using the radiotracers 109Cd and 65Zn. A compartmental kinetic model was constructed and parametrized by fitting the model to metal body concentrations. Using the pharmacokinetic modeling approach and taking into account the distribution of the metal between water and sediment, the different routes were quantitatively separated. Under the experimental conditions, the sediment phase accounted for 9.8% of the cadmium and 52% of the zinc uptake. These values are based on the uptake of the radiotracers spiked sediments and therefore likely represent maximal values since it was shown that under the specific conditions this was the most mobile metal fraction. This difference was largely explained by the large difference in assimilation efficiency between cadmium and zinc. Simulations of different conditions showed that both dissolved and sediment-associated metal can be important sources of metal exposure for the worms and that the relative importance strongly depends on the metal and exposure conditions including the lability of the metals in the sediment phase.     

Impact of pH on Cu accumulation kinetics in earthworm cytosol

We studied the interaction between toxic stress and accumulation in the earthworm Aporrectodea caliginosa, as induced by different soil copper pools and soil constituents (especially pH). Earthworms were exposed in quartz sand, spiked soils, and field soils with different Cu concentrations and varying soil composition. The copper content in the earthworms was determined in the following: the cytosolic fraction, a granular fraction and a fraction consisting of tissue fragments, cell membranes and intact cells. The highest amount of Cu was found in the cytosolic fraction. The other fractions varied only slightly in response to changes in any of the copper pools in soil. Cytosolic copper was the best predictor of Cu availability to earthworms collected from soils at constant pH, as statistically significant correlations were obtained with pore water pCu at constant pH in earthworms exposed in quartz sand. This correlation was lost for cytosolic Cu concentrations in earthworms exposed to spiked soils and field soils at differing pHs. Instead, cytosolic copper correlated well to Cu in either pore water or solid phase. Soil pH not only plays an important role in the availability of metals and therefore on their uptake fluxes, but internal competition of Cu2+ and H+ at physiologically active binding sites also explained these apparent contradictions and increased the predictability of body burdens significantly.     

Role of sediment resuspension in the remobilization of particulate-phase metals from coastal sediments

The release of particulate-phase trace metals due to sediment resuspension has been investigated by combining erosion chamber experiments that apply a range of shear stresses typically encountered in coastal environments with a shear stress record simulated by a hydrodynamic model. Two sites with contrasting sediment chemistry were investigated. Sediment particles enriched in silver, copper, and lead, 4-50 times greater than the bulk surface-sediment content, were the first particles to be eroded. As the shear-stress level was increased in the chamber, the total mass eroded increased, butthe enrichment of these trace metals fell, approaching the bulk-sediment content. From the temporal distribution of shear stress generated by the hydrodynamic model for a site in Boston Harbor, resuspension fluxes were estimated. The erosion threshold of this site is exceeded during spring tides, releasing the particles enriched in trace metals into the water column. Due to the higher trace metal content and the regularity of resuspension, low-energy resuspension events (up to a shear stress of 0.2 N/m(2)) contribute up to 60% of the resuspension metal flux in an average year. The estimated annual quantity of copper and lead resuspended into the water column is higher than estimates of the total riverine flux for these metals. These results indicate that sediment resuspension is a very important mechanism for releasing metals into the water column and provide new insight into the chemical and physical processes controlling the long-term fate of trace metals in contaminated sediments.     

Bioaccessibility of metal cations in soil is linearly related to its water exchange rate constant

Site-specific risk assessments often incorporate the concepts of bioaccessibility (i.e., contaminant fraction released into gastrointestinal fluids) or bioavailability (i.e., contaminant fraction absorbed into systemic circulation) into the calculation of ingestion exposure. We evaluated total and bioaccessible metal concentrations for 19 soil samples under simulated stomach and duodenal conditions using an in vitro gastrointestinal model. We demonstrated that the median bioaccessibility of 23 metals ranged between <1 and 41% under simulated stomach conditions and < 1 and 63% under simulated duodenal conditions. Notably, these large differences in metal bioaccessibility were independent of equilibrium solubility and stability constants. Instead, the relationship (stomach phase R = 0.927; duodenum phase R = 0.891) between bioaccessibility and water exchange rates of metal cations (k(H?O)) indicated that desorption kinetics may influence if not control metal bioaccessibility.     

Enrichment of heavy metals in sediment resulting from soil erosion on agricultural fields

Heavy metal pollution of soil and water is often associated with industry, but in this paper we demonstrate that water erosion on agricultural soil which has received only agrochemicals has enriched sediment metal concentrations to toxic levels which breach many accepted standards for soils and sediments. Eight 0.1 ha erosion plots with different cultivation treatments were monitored over a 6 year period for surface runoff, soil loss, and Cr, Cu, Pb, and Ni concentrations. Mean concentrations of these heavy metals were up to 3.98 times higher in the sediment than in the parent soil and in some erosion events the sediment had 13.5 times the concentration of metals in the soil. All the sediment heavy metal concentrations were significantly correlated (p < 0.01) with the clay and silt sized fractions of the sediment and with carbon content. The erosion was a highly selective process enriching the detached material in silt, clay, and organic carbon. This was particularly true in smaller erosion events. Sediment metal concentrations tended to follow the shape of runoff hydrographs, although the pattern changed from storm to storm.     

Assessing the effectiveness of thin-layer sand caps for contaminated sediment management through passive sampling

The effectiveness of thin-layer sand capping for contaminated sediment management (capping with a layer of thickness comparable to the depth of benthic interactions) is explored through experiments with laboratory-scale microcosms populated with the deposit-feeding oligochaete, Ilyodilus templetoni. Passive sampling of pore water concentrations in the microcosms using polydimethylsiloxane (PDMS)-coated fibers enabled quantification of high-resolution vertical concentration profiles that were used to infer contaminant migration rates and mechanisms. Observed concentration profiles were consistent with models that combine traditional contaminant transport processes (sorption-retarded diffusion) with bioturbation. Predictions of bioaccumulation based on contaminant pore water concentrations within the surface layer of the cap correlated well with observed bioaccumulation (correlation coefficient of 0.92). The results of this study show that thin-layer sand caps of contaminated sediments can be effective at reducing the bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) provided the thickness of the cap layer exceeds the depth of organism interaction with the sediments and the pore water concentrations within the biologically active zone remain low (e.g., when molecular diffusion controls transport from the underlying sediment layer).     

Dissolved PCBs, PAHs, and HCB in pore waters and overlying waters of contaminated harbor sediments

Aqueous concentrations of polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs), pentachlorobenzene, and hexachlorobenzene (HCB) were determined by exposing low-density polyethylene (LDPE) strips to the pore waters and the overlying water in two contaminated harbors. LDPE strips were also exposed in the laboratory to sediment slurries and to stagnant sediments collected at the same locations. Surprisingly short equilibration time scales (1-60 days for log K(ow) < 7) were observed for the exposures to sediment slurries. This was a result of a profound decrease in transport resistance, due to the presence of particles in the aqueous boundary layer. Concentrations in the pore water were calculated from the initial uptake rates and the dissipation rates of performance reference compounds. Good correspondence existed with concentrations estimated from the equilibrium amounts in the strips and LDPE-water partition coefficients. Sediment-water partition coefficients for PAHs were higher than for PCBs and chlorobenzenes by approximately 1 order of magnitude. A one-dimensional diffusion model was used to describe contaminant uptake by LDPE strips from stagnant sediments. The results indicated that 95% of the PAHs and 50% of the PCBs were immobile on a time scale of two months. A comparison of concentrations in pore waters and water columns indicated that a fair degree of equilibrium existed for PCBs and that one sediment was a potential source of PAHs. Concentrations of HCB near a former discharge site were higher by a factor of 6 compared to reference locations.     

Are accumulated sulfide-bound metals metabolically available in the benthic oligochaete Tubifex tubifex?

The present study evaluates the relationship between metal-binding sediment characteristics like acid volatile sulfides (AVS), metal accumulation, and internal metal distribution in the benthic oligochaete Tubifex tubifex and relates this accumulation to the induction of metallothionein-like proteins (MTLPs). In total, 15 Flemish lowland rivers were sampled. Cd, Cu, Zn, Pb, Ni, As, Cr, Co, and Ag concentrations were measured in environmental fractions (water and sediment) and worm tissue (both total and subcellular fractions). Furthermore, total cytosolic MTLP concentrations were measured in the worm tissue. Our results showed that Cd, Pb, Ni, and Cr were mainly stored as biological detoxified metal (BDM) while Cu, Zn, As, and Ag were mostly available in the metal sensitive fraction (MSF). A remarkable difference in the subcellular distribution of accumulated Cd, Ni, and Co between anoxic (SEMMe-AVS<0; mostly stored as BDM) and oxic (SEMMe-AVS>0; mostly stored in the MSF) sediments was noticed. Moreover, a rapid increase in MTLP induction was found when SEMTot-AVS>0. Our results indicate that the accumulated sulfide-bound metals were detoxified and little available to the metabolism of T. tubifex under anoxic conditions.     

Natural occurrence of hexavalent chromium in the Aromas Red Sands Aquifer, California

To address increasing concerns of chromium contamination in the drinking water of Santa Cruz County, we designed a study to investigate the source(s) and spatial gradients of the chromium concentration and speciation in local aquifers. This study was catalyzed by a report (January 2001) bythe Soquel Creek Water District of elevated hexavalent chromium concentrations ranging from 6 to 36 microg L(-1), approaching the state's maximum concentration limit of 50 microg L(-1), in the Aromas Red Sands aquifer. To test the accuracy of those preliminary measurements, we collected groundwater using trace metal clean techniques from 11 sites in Santa Cruz County, including 10 from the aquifer with reportedly elevated chromium concentrations and 1 from an adjacent aquifer, the Purisima, and analyzed them fortotal chromium using inductively couple plasma mass spectrometry. Nine of the reportedly 10 contaminated sites had total chromium concentrations ranging from 5 to 39 microg L(-1), while one from the control site was below the limit of detection (0.01 microg L(-1)). We also measured the speciation of chromium at all sites using a solid supported membrane extraction coupled with graphite furnace atomic absorption spectrometry and determined that on average 84% of total chromium was Cr(VI). In addition to the groundwater analyses, a series of extractions were performed on sediment samples from both the Aromas Red Sands and Purisima aquifers. These tests were used to empirically characterize sediment trace metal (Cr, Fe, Mn) distributions in five phases providing information about the origin, availability, reactivity, and mobilization of these trace metals. Results from groundwater and sediment samples indicate that the chromium is naturally occurring in the Aromas Red Sands aquifer, possibly by Cr(III) mineral deposits being oxidized to Cr(VI) by manganese oxides in the aquifer.     

Trace metal levels in uncontaminated groundwater of a coastal watershed: importance of colloidal forms

Groundwater and surface water were collected using trace metal clean techniques from the upper glacial aquifer of West Neck Bay (Shelter Island) in eastern Long Island, NY, during the late spring and summer of 1999. The collection sites on Shelter Island are located in an area that is primarily residential and believed to have uncontaminated groundwater. Ultrafiltration was used to size-fractionate the dissolved (<0.45 microm) fraction into colloidal (1 kDa - 0.45 microm) and low molecular weight (<1 kDa) size pools. These fractions were analyzed for trace metals (Al, Ag, Cd, Cu, Mn, Pb, and Zn), organic carbon, and inorganic nutrients (NH4, NO3, PO4). The levels of metals and organic carbon in the groundwater were as low as those found in the open ocean, far removed from anthropogenic inputs. These findings corroborate the need to apply trace metal clean techniques in the determination of metal levels in uncontaminated groundwater. A significant fraction of dissolved metals (22-96%) and organic carbon (approximately 40%) in the groundwater and in surface waters of the Bay was found to be associated with colloids. The significance of the metal association with the colloidal fraction decreased in the order of Al > Cu > Ag > Zn = Cd = Mn and appeared to be dependent on the affinities of these metals for humic substances. In contrast, NO3 and NH4 were found to be almost entirely (approximately 98-99%) in the low molecular weight size fraction. Metal/aluminum and metal/carbon ratios measured in the colloids were similar to those reported for humic substances and significantly different from those of soils. This suggests that colloidal particles might originate from humic materials as opposed to purely inorganic minerals. These results indicate the need to consider the colloidal fraction in the fate and mobility of metals in groundwater and that, despite the low levels of organic matter (<50 microM of DOC) measured in groundwater, some groundwater colloids appear to be organic in nature.