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Measurement of the total iron content of a sample is useful as a background datum against which to compare <br /> changes in the dissolved concentration <br /> Sulfate Sulfate is derived primarily from soil minerals The occurrence of sulfate reduction may be inferred from <br /> the presence of black acid volatile sulfide deposits on materials in long-term contact with contaminated <br /> groundwater(Barker et al, 1995) Pyrite may be precipitated in the soil Sulfate concentrations in groundwater are <br /> naturally higher than those for nitrate Sulfate concentrations of 100 mg/L might be considered moderate and <br /> several hundred mg/L is not uncommon Concentrations below 40 mg/L are indicative of methanogemc conditions <br /> (Cookson, 1995) Sulfate reduction typically occurs when Eh is approximately-200 mV <br /> Methanogenesis Under methanogemc conditions (Eh of approximately -250 mV), carbon dioxide and methane <br /> are both produced by hydrocarbon oxidation The utility of measurement of these compounds is discussed below <br /> (metabolic end-products) <br /> Carbonate/Hardness/Total alkalinity <br /> One of these associated analyses is typically conducted at the laboratory on collected water samples Increased <br /> carbonate concentration will commonly occur where acidity dissolves carbonates from the soil Sufficient <br /> concentrations of carbonate will buffer the pH and prevent acid toxicity that may result from hydrocarbon <br /> degradation Total alkalinity (as carbonate) concentrations exceeding 100 mg/L may be considered conducive to <br /> effective buffering Dissolved carbon dioxide may be assessed in conjunction with total alkalinity analysis <br /> Metabolic end-products <br /> Metabolic end-products of hydrocarbon biodegradation include carbon dioxide, water, nitrogen, nitrites, ferrous <br /> iron, sulfites, sulfides, hydrogen sulfide, and methane Carbon dioxide, hydrogen sulfide and methane may be <br /> measured with a gas meter at the wellhead Reduced ferrous iron, sulfite and sulfide may be analyzed in water <br /> samples Sulfides may precipitate into the soil and be under-represented in groundwater samples Nitrite is <br /> metastable and therefore nitrite detection (generally <0 1 mg/L) is indicative of ongoing denitrification <br /> . Ammonium ions in excess of 10 mg/L may also be indicative of anaerobic conditions Elevated concentrations of <br /> all metabolic end-products should correlate positively with elevated hydrocarbons <br /> Field measurement of dissolved carbon dioxide (DCD) is of secondary importance but may provide useful data <br /> Dissolved carbon dioxide is derived primarily from the atmosphere Elevated DCD spatially correlated with <br /> decreased DO concentration, may be indicative of aerobic microbial hydrocarbon degradation as DCD is a <br /> metabolic end-product Elevated DCD may also result from anaerobic degradation High background DCD is a <br /> desirable feature in terms of the capacity of the groundwater to buffer decreases in pH produced by microbial <br /> hydrocarbon degradation which may otherwise limit biological activity Carbon dioxide is more soluble than <br /> oxygen and average concentrations are around an order of magnitude higher <br /> Contaminant Fate and Transport Modeling <br /> Plume transport can be modeled using simple analytical equations Transport assuming no attenuation can be <br /> modeled and the results compared with field data to provide a preliminary indication of the extent of natural <br /> attenuation Transport models can be modified to include various natural attenuation factors based on actual site <br /> data Comparison of these modeling results to actual field results can be used to confirm natural attenuation <br /> To model plume transport,the following basic site characteristics need to be determined <br /> • Historical dissolved hydrocarbon distribution <br /> • Hydraulic conductivity <br /> • Soil density/porosity <br /> • Aquifer thickness <br /> • Groundwater gradient/depth fluctuations <br /> • Possible preferential migration pathways <br /> Organic content of the soil, foc <br /> CLEARWATER GROUP(NATURAL ATTENUATION) 5 revised October 3,2002 <br />