Brian A. Bergamaschi

The effect of grain size and surface area on organic matter, lignin and carbohydrate concentration, and molecular compositions in Peru Margin sediments

A C-rich sediment sample from the Peru Margin was sorted into nine hydrodynamically- determined grain size fractions to explore the effect of grain size distribution and sediment surface area on organic matter content and composition. The neutral monomeric carbohydrate composition, lignin oxidation product yields, total organic carbon, and total nitrogen contents were determined independently for each size fraction, in addition to sediment surface area and abundance of biogenic opal. The percent organic carbon and percent total nitrogen were strongly related to surface area in these sediments. In turn, the distribution of surface area closely followed mass distribution among the textural size classes, suggesting hydrodynamic controls on grain size also control organic carbon content. Never- theless, organic compositional distinctions were observed between textural size classes. Total neutral carbohydrate yields in the Peru Margin sediments were found to closely parallel trends in total organic carbon, increasing in abundance among grain size fractions in proportion to sediment surface area. Coincident with the increases in absolute abundance, rhamnose and mannose increased as a fraction of the total carbohydrate yield in concert with surface area, indicating these monomers were preferentially represented in carbohydrates associated with surfaces. Lignin oxidation product yields varied with surface area when normalized to organic carbon, suggesting that the terrestrially-derived component may be diluted by sorption of marine derived material. Lignin-based parameters suggest a separate source for terrestrially derived material associated with sand-size material as opposed to that associated with silts and clays. Copyright 0 1997 Elsevier Science Ltd

Tannin diagenesis in mangrove leaves from a tropical estuary: A novel molecular approach

Molecular-level condensed tannin analyses were conducted on a series of mangrove ( Rhizophora mangle) leaves at various stages of decomposition in a tropical estuary. Total molecular tannin yields ranged from 0.5% ash-free dry weight (AFDW) in the most highly degraded black leaves (6 -7 weeks in the water) up to .7% AFDW in fresh leaves (,1 week in the water). Total tannin exhibits an intermediate lability in these leaves relative to other measured biochemicals. Leaching is an important mechanism in tannin removal from leaves as indicated by the 30% loss of measurable tannin during a leaching experiment. Condensed tannin was .80% procyanidin (PC) with the remainder being prodelphinidin (PD). PD tannin, with its higher degree of hydroxylation, proved to be more labile than PC tannin. Average chain length of condensed tannin (degree of polymerization) exhibited an initial increase in response to leaching, but later decreased in the subsequent shift toward abiotic or microbially mediated chemical reactions. Several trends point toward a possible condensation reaction in which tannin plays a role in nitrogen immobilization. These include an apparent inverse correlation between molecular tannin and nitrogen, a positive correlation between molecular tannin and percent basic amino acids, 13 C-NMR data indicating transformation of tannin as opposed to remineralization, and 13 C-NMR data showing loss of condensed tannin B-ring phenolic carbons coupled with preservation of A-ring phenolic carbon. In addition to condensed tannin, the molecular method used also yielded several triterpenoids. Triterpenoids accounted for up to 3.5% AFDW of the leaf material and exhibited a threefold increase between yellow senescent leaves entering the estuary and black leaves. This trend is likely due to the weakening of protective cuticular membranes during leaf decomposition, which leads to increased yields in the acidic conditions used for tannin analyses. Copyright

Use and Environmental Occurrence of Antibiotics in Freestall Dairy Farms with Manured Forage Fields

Environmental releases of antibiotics from concentrated animal feeding operations (CAFOs) are of increasing regulatory concern. This study investigates the use and occurrence of antibiotics in dairy CAFOs and their potential transport into first-encountered groundwater. On two dairies we conducted four seasonal sampling campaigns, each across 13 animal production and waste management systems and associated environmental pathways: application to animals, excretion to surfaces, manure collection systems, soils, and shallow groundwater. Concentrations of antibiotics were determined using on line solid phase extraction (OLSPE) and liquid chromatography-tandem mass spectrometry (LC/MS/MS) with electrospray ionization (ESI) for water samples, and accelerated solvent extraction (ASE) LC/MS/MS with ESI for solid samples. A variety of antibiotics were applied at both farms leading to antibiotics excretion of several hundred grams per farm per day. Sulfonamides, tetracyclines, and their epimers/isomers, and lincomycin were most frequently detected. Yet, despite decades of use, antibiotic occurrence appeared constrained to within farm boundaries. The most frequent antibiotic detections were associated with lagoons, hospital pens, and calf hutches. When detected below ground, tetracyclines were mainly found in soils, whereas sulfonamides were found in shallow groundwater reflecting key differences in their physicochemical properties. In manure lagoons, 10 compounds were detected including tetracyclines and trimethoprim. Of these 10, sulfadimethoxine, sulfamethazine, and lincomycin were found in shallow groundwater directly downgradient from the lagoons. Antibiotics were sporadically detected in field surface samples on fields with manure applications, but not in underlying sandy soils. Sulfadimethoxine and sulfamethazine were detected in shallow groundwater near field flood irrigation gates, but at highly attenuated levels.

Comparative analyses of DOC and DON in natural waters

Abstract Extensive comparisons of the measured dissolved organic carbon (DOC) and nitrogen (DON) contents of four different natural waters were carried out prior to the Seattle DOC/DON Workshop in July 1991 to assess the current variability in these measurements among aquatic scientists. This study included 34 DOC analyses with over 20 different instruments and 13 DON analyses of the same samples using nine different instruments. In spite of good precision for individual instruments (5.9% average sample mean deviation), independently measured DOC concentrations of the same water ranged over an order of magnitude and varied on average approximately ±40% of the mean value. Variability among similar instruments operated in different labs ( ± 15–42% of the mean) was almost as large. This observation plus evidence for constant offsets among DOC analyses made in different labs suggest that unaccounted for blanks contribute more toward the observed variability than other instrument characteristics such as oxidation method, catalyst or oven temperature. The corresponding relative analytical precisions for total dissolved nitrogen and DON were 6.8% and 27%, respectively. Independent measurements of DON varied on average ±30% of the mean value and could not be related to instrument characteristics within this highly variable data set. During the Workshop, manufacturers of four different DOC analyzers measured the DOC content of untreated and spiked lake and seawater samples using common blank and calibration procedures. Excellent agreement was obtained, supporting indications from the pre-workshop exercise that operator-dependent factors, such as blank determination and treatment, are more important sources of measurement variability than instrument design.

Tidally driven export of dissolved organic carbon, total mercury, and methylmercury from a mangrove-dominated estuary

The flux of dissolved organic carbon (DOC) from mangrove swamps accounts for 10% of the global terrestrial flux of DOC to coastal oceans. Recent findings of high concentrations of mercury (Hg) and methylmercury (MeHg) in mangroves, in conjunction with the common co-occurrence of DOC and Hg species, have raised concerns that mercury fluxes may also be large. We used a novel approach to estimate export of DOC, Hg, and MeHg to coastal waters from a mangrove-dominated estuary in Everglades National Park (Florida, USA). Using in situ measurements of fluorescent dissolved organic matter as a proxy for DOC, filtered total Hg, and filtered MeHg, we estimated the DOC yield to be 180 (±12.6) g C m–2 yr–1, which is in the range of previously reported values. Although Hg and MeHg yields from tidal mangrove swamps have not been previously measured, our estimated yields of Hg species (28 ± 4.5 μg total Hg m–2 yr–1 and 3.1 ± 0.4 μg methyl Hg m–2 yr–1) were five times greater than is typically reported for terrestrial wetlands. These results indicate that in addition to the well documented contributions of DOC, tidally driven export from mangroves represents a significant potential source of Hg and MeHg to nearby coastal waters.

Environmental occurrence and shallow ground water detection of the antibiotic monensin from dairy farms

Pharmaceuticals used in animal feeding operations have been detected in various environmental settings. There is a growing concern about the impact on terrestrial and aquatic organisms and the development of antibiotic-resistant strains of microorganisms. Pharmaceutical use in milking cows is relatively limited compared with other livestock operations, except for the ionophore monensin, which is given to lactating cows as a feed. By weight, monensin can be the most significant antibiotic used in a dairy farm. This study investigates the potential of monensin to move from dairy operations into the surrounding ground water. Using two dairy farms in California as study sites, we twice collected samples along the environmental pathway-from flush lanes, lagoon waters, and shallow ground water beneath the dairies and beneath its associated manured fields. Monensin concentrations were determined using solid-phase extraction and liquid chromatography-tandem mass spectrometry with positive electrospray ionization. Monensin was detected in all of the flush lane and lagoon water samples. Theoretical maximum concentration estimated from the actual dosing rate and the theoretical excretion rate assuming no attenuation was one order of magnitude greater than observed concentrations, suggesting significant attenuation in the manure collection and storage system. Monensin was also detected, at levels ranging from 0.04 to 0.39 microg L(-1), in some of the ground water samples underneath the production area of the dairy but not from the adjacent manured fields. Concentrations in ground water immediately downgradient of the lagoons were one to two orders of magnitude lower than the concentrations detected in lagoons, suggesting attenuation in the subsurface. The data suggest the possibility of monensin transport into shallow (2-5 m) alluvial ground water from dairy management units, including manure storage lagoons and freestalls occupied by heifers, lactating cows, and dry cows.

Mississippi River Nitrate Loads from High Frequency Sensor Measurements and Regression-Based Load Estimation

Accurately quantifying nitrate (NO3-) loading from the Mississippi River is important for predicting summer hypoxia in the Gulf of Mexico and targeting nutrient reduction within the basin. Loads have historically been modeled with regression-based techniques, but recent advances with high frequency NO3- sensors allowed us to evaluate model performance relative to measured loads in the lower Mississippi River. Patterns in NO3- concentrations and loads were observed at daily to annual time steps, with considerable variability in concentration-discharge relationships over the two year study. Differences were particularly accentuated during the 2012 drought and 2013 flood, which resulted in anomalously high NO3- concentrations consistent with a large flush of stored NO3- from soil. The comparison between measured loads and modeled loads (LOADEST, Composite Method, WRTDS) showed underestimates of only 3.5% across the entire study period, but much larger differences at shorter time steps. Absolute differences in loads were typically greatest in the spring and early summer critical to Gulf hypoxia formation, with the largest differences (underestimates) for all models during the flood period of 2013. In additional to improving the accuracy and precision of monthly loads, high frequency NO3- measurements offer additional benefits not available with regression-based or other load estimation techniques.

Pesticides Associated with Suspended Sediments Entering San Francisco Bay Following the First Major Storm of Water Year 1996

Estuaries receive large quantities of suspended sediments following the first major storm of the water year. The first-flush events transport the majority of suspended sediments in any given year, and because of their relative freshness in the hydrologic system, these sediments may carry a significant amount of the sediment-associated pesticide load transported into estuaries. To characterize sediment-associated pesticides during a first-flush event, water and suspended sediment samples were collected at the head of the San Francisco Bay during the peak in suspended sediment concentration that followed the first major storm of the 1996 hydrologic year. Samples were analyzed for a variety of parameters as well as 19 pesticides and degradation products that span a wide range of hydrophobicity. Tidal mixing at the head of the estuary mixed relatively fresh suspended sediment transported down the rivers with suspended sediments in estuary waters. Segregation of the samples into groups with similar degrees of mixing between river and estuary water revealed that transport of suspended sediments from the Sacramento-San Joaquin drainage basin strongly influenced the concentration and distribution of sediment-associated pesticides entering the San Francisco Bay. The less-mixed suspended sediment contained a different distribution of pesticides than the sediments exposed to greater mixing. Temporal trends were evident in pesticide content after samples were segregated according to mixing history. These results indicate sampling strategies that collect at a low frequency or do not compare samples with similar mixing histories will not elucidate basin processes. Despite the considerable influence of mixing, a large number of pesticides were found associated with the suspended sediments. Few pesticides were found in the concurrent water samples and in concentrations much lower than predicted from equilibrium partitioning between the aqueous and sedimentary phases. The observed sediment-associated pesticide concentrations may reflect disequilibria between sedimentary and aqueous phases resulting from long equilibration times at locations where pesticides were applied, and relatively short transit times over which re-equilibration may occur.

Concurrent photolytic degradation of aqueous methylmercury and dissolved organic matter.

Monomethyl mercury (MeHg) is a potent neurotoxin that threatens ecosystem viability and human health. In aquatic systems, the photolytic degradation of MeHg (photodemethylation) is an important component of the MeHg cycle. Dissolved organic matter (DOM) is also affected by exposure to solar radiation (light exposure) leading to changes in DOM composition that can affect its role in overall mercury (Hg) cycling. This study investigated changes in MeHg concentration, DOM concentration, and the optical signature of DOM caused by light exposure in a controlled field-based experiment using water samples collected from wetlands and rice fields. Filtered water from all sites showed a marked loss in MeHg concentration after light exposure. The rate of photodemethylation was 7.5×10(-3)m(2)mol(-1) (s.d. 3.5×10(-3)) across all sites despite marked differences in DOM concentration and composition. Light exposure also caused changes in the optical signature of the DOM despite there being no change in DOM concentration, indicating specific structures within the DOM were affected by light exposure at different rates. MeHg concentrations were related to optical signatures of labile DOM whereas the percent loss of MeHg was related to optical signatures of less labile, humic DOM. Relationships between the loss of MeHg and specific areas of the DOM optical signature indicated that aromatic and quinoid structures within the DOM were the likely contributors to MeHg degradation, perhaps within the sphere of the Hg-DOM bond. Because MeHg photodegradation rates are relatively constant across freshwater habitats with natural Hg-DOM ratios, physical characteristics such as shading and hydrologic residence time largely determine the relative importance of photolytic processes on the MeHg budget in these mixed vegetated and open-water systems.

Microbial degradation of plant leachate alters lignin phenols and trihalomethane precursors

Although the importance of vascular plant-derived dissolved organic carbon (DOC) in freshwater systems has been studied, the role of leached DOC as precursors of disinfection byproducts (DBPs) during drinking water treatment is not well known. Here we measured the propensity of leachates from four crops and four aquatic macrophytes to form trihalomethanes (THMs)-a regulated class of DBPs-before and after 21 d of microbial degradation. We also measured lignin phenol content and specific UV absorbance (SUVA(254)) to test the assumption that aromatic compounds from vascular plants are resistant to microbial degradation and readily form DBPs. Leaching solubilized 9 to 26% of total plant carbon, which formed 1.93 to 6.72 mmol THM mol C(-1). However, leachate DOC concentrations decreased by 85 to 92% over the 21-d incubation, with a concomitant decrease of 67 to 92% in total THM formation potential. Carbon-normalized THM yields in the residual DOC pool increased by 2.5 times on average, consistent with the preferential uptake of nonprecursor material. Lignin phenol concentrations decreased by 64 to 96% over 21 d, but a lack of correlation between lignin content and THM yields or SUVA(254) suggested that lignin-derived compounds are not the source of increased THM precursor yields in the residual DOC pool. Our results indicate that microbial carbon utilization alters THM precursors in ecosystems with direct plant leaching, but more work is needed to identify the specific dissolved organic matter components with a greater propensity to form DBPs and affect watershed management, drinking water quality, and human health.