Concentrations of perfluorinated chemicals (PFCs) were measured in surface waters and sediments from the Coosa River watershed in northwest Georgia, USA, to examine their distribution downstream of a suspected source. Samples from eight sites were analyzed using liquid chromatography-tandem mass spectrometry. Sediments were also used in 28-d exposures with the aquatic oligochaete, Lumbriculus variegatus, to assess PFC bioaccumulation. Concentrations of PFCs in surface waters and sediments increased significantly below a land-application site (LAS) of municipal/industrial wastewater and were further elevated by unknown sources downstream. Perfluorinated carboxylic acids (PFCAs) with eight or fewer carbons were the most prominent in surface waters. Those with 10 or more carbons predominated sediment and tissue samples. Perfluorooctane sulfonate (PFOS) was the major homolog in contaminated sediments and tissues. This pattern among sediment PFC concentrations was consistent among sites and reflected homolog concentrations emanating from the LAS. Concentrations of PFCs in oligochaete tissues revealed patterns similar to those observed in the respective sediments. The tendency to bioaccumulate increased with PFCA chain length and the presence of the sulfonate moiety. Biota-sediment accumulation factors indicated that short-chain PFCAs with fewer than seven carbons may be environmentally benign alternatives in aquatic ecosystems; however, sulfonates with four to seven carbons may be as likely to bioaccumulate as PFOS.
Manganese is a toxic element frequently overlooked when assessing toxicity of effluents, sediments, and pore waters. Manganese can be present at toxic levels in anoxic solutions due to increased solubility under chemically reducing conditions, and it can remain at those levels for days in aerated test waters due to slow precipitation kinetics. Ceriodaphnia dubia and Hyalella azteca are freshwater organisms often used for toxicity testing and recommended for assessments of effluents and pore waters. Lethal and reproductive-inhibition concentrations of Mn were determined for C. dubia in acute 48-h tests and chronic three-brood tests using animals <24 h old and between 24 and 48 h old. Sensitivity of H. azteca to Mn was determined with 7-day-old animals in acute 96-h tests. Tests were run at three levels of water hardness to assess the amelioratory effect, which was often significant. Manganese concentrations were measured analytically at test initiation and after 96 h for calculation of toxicity and determination of Mn precipitation during the tests. Minimal amounts of Mn (=3%) precipitated within 96 h. LC(50)s determined for H. azteca progressively increased from 3.0 to 8.6 to 13.7 mg Mn/L in soft, moderately hard, and hard waters, respectively. The tolerance of C. dubia to Mn was not significantly different between moderately hard and hard waters, but was significantly lower in soft water. Manganese sensitivity of C. dubia was not significantly different between the ages tested. Acute LC(50) values for C. dubia averaged 6. 2, 14.5 and 15.2 mg Mn/L and chronic IC(50) values averaged 3.9, 8.5 and 11.5 mg Mn/L for soft, moderately-hard and hard waters, respectively. Manganese toxicity should be considered when assessing solutions with concentrations approaching these levels.
Sediment pore water has the potential to yield important information on sediment quality, but the influence of isolation procedures on the chemistry and toxicity are not completely known and consensus on methods used for the isolation from sediment has not been reached. To provide additional insight into the influence of collection procedures on pore water chemistry, anion (filtered only) and cation concentrations were measured in filtered and unfiltered pore water isolated from four sediments using three different procedures: dialysis, centrifugation, and vacuum. Peepers were constructed using 24-cell culture plates and cellulose membranes and vacuum extractors consisted of fused-glass air stones attached with airline tubing to 60-cc syringes. Centrifugation was accomplished at two speeds (2,500 and 10,000 g) for 30 min in a refrigerated centrifuge maintained at 4 degreesC. Only minor differences in chemical characteristics and cation and anion concentrations were found among the different collecting methods with differences being sediment-specific. Filtering of the pore water did not appreciably reduce major cation concentrations, but trace metals (Cu and Pb) were markedly reduced. Although the extraction methods evaluated produced pore waters of similar chemistries, the vacuum extractor provided the following advantages over the other methods: ease of extraction, volumes of pore water isolated, minimal preparation time, and least time required for extraction of pore water from multiple samples at one time.
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