Mg isotope constraints on soil pore-fluid chemistry: Evidence from Santa Cruz, California

Mg isotope ratios (²⁶Mg/²⁴Mg) are reported in soil pore-fluids, rain and seawater, grass and smectite from a 90 kyr old soil, developed on an uplifted marine terrace from Santa Cruz, California. Rain water has an invariant ²⁶Mg/²⁴Mg ratio (expressed as δ²⁶Mg) at −0.79 ± 0.05‰, identical to seawater δ²⁶Mg. Detrital smectite (from the base of the soil profile, and therefore unweathered) has a δ²⁶Mg value of 0.11‰, potentially enriched in ²⁶Mg by up to 0.3‰ compared to the bulk silicate Earth Mg isotope composition (although within the range of all terrestrial silicates). The soil pore-waters show a continuous profile with depth for δ²⁶Mg, ranging from −0.99‰ near the surface to −0.43‰ at the base of the profile. Shallow pore-waters (<1 m) have δ²⁶Mg values that are similar to, or slightly lower than the rain waters. This implies that the degree of biological cycling of Mg in the pore-waters is relatively small and is quantified as <32%, calculated using the average Mg isotope enrichment factor between grass and rain (δ²⁶Mg_grass-δ²⁶Mg_rain) of 0.21‰. The deep pore-waters (1-15 m deep) have δ²⁶Mg values that are intermediate between the smectite and rain, ranging from −0.76‰ to −0.43‰, and show a similar trend with depth compared to Sr isotope ratios. The similarity between Sr and Mg isotope ratios confirms that the Mg in the pore-waters can be explained by a mixture between rain and smectite derived Mg, despite the fact that Mg and Sr concentrations may be buffered by the exchangeable reservoir. However, whilst Sr isotope ratios in the pore-waters span almost the complete range between mineral and rain inputs, Mg isotopes compositions are much closer to the rain inputs. If Mg and Sr isotope ratios are controlled uniquely by a mixture, the data can be used to estimate the mineral weathering inputs to the pore-waters, by correcting for the rain inputs. This isotopic correction is compared to the commonly used chloride correction for precipitation inputs. A consistent interpretation is only possible if Mg isotope ratios are fractionated either by the precipitation of a secondary Mg bearing phase, not detected by conventional methods, or selective leaching of ²⁴Mg from smectite. There is therefore dual control on the Mg isotopic composition of the pore-waters, mixing of two inputs with distinct isotopic compositions, modified by fractionation. The data provide (1) further evidence for Mg isotope fractionation at the surface of the Earth and (2) the first field evidence of Mg isotope fractionation during uptake by natural plants. The coherent behaviour of Mg isotope ratios in soil environments is encouraging for the development of Mg isotope ratios as a quantitative tracer of both weathering inputs of Mg to waters, and the physicochemical processes that cycle Mg, a major cation linked to the carbon cycle, during continental weathering.     

Seasonal dynamics of CO2 profiles across a soil chronosequence,Santa Cruz,California

Concentrations of CO₂ in soil atmosphere and CO₂ efflux were measured across a marine terrace soil chronosequence near Santa Cruz, California. Soil development, specifically the formation of an argillic horizon, has created a two-tier soil gas profile in the older terrace soils. The soil above the argillic horizon has seasonal variations in soil CO₂ associated with plant respiration. The older soils with dense argillic horizons maintain a year round ～1%CO₂ below the argillic horizon. The CO₂efflux during the growing season is higher on the older terraces.     

Effects of the Santa Cruz harbor on coastal processes of northern Monterey Bay,California

An average of 230,000 cubic meters of sand is provided to the beaches of northern Monterey Bay each year by littoral transport from upcoast and from local river input. Two jetties constructed as part of a small craft harbor interrupted the littoral flow of sand and significantly altered the area's natural coastal processes. A wide protective beach immediately formed upcoast against a formerly retreating beach cliff. Sand now filling the harbor mouth each winter has led to expensive yearly dredging as well as seasonally or permanently depleted downcoast beaches. Seacliff retreat, always a problem in the area, is caused primarily by surf attack of weaker stratigraphic units and erosion along joint sets and faults, causing collapse of the bluffs. The seasonal loss of protective beaches has led to a two- to three-fold increase in the rate of downcoast cliff retreat following harbor construction except where protective rip-rap has been emplaced by property owners.     

Hydrological Modeling and Prehistoric Settlement on Santa Rosa Island,California, USA

Fresh water availability was an important variable that influenced prehistoric human settlement on California's northern Channel Islands. Previous attempts to understand settlement on the islands use watershed size as a proxy for water at canyon mouths. In semi‐arid regions, this approach has limitations because streams may lose much or all of their flow to groundwater. We developed a distributed hydrological model for Santa Rosa Island that incorporates geospatial and temporal data for climate (precipitation, solar radiation, wind speed, relative humidity, temperature), soils, vegetation, and topography to simulate the complex land‐surface‐groundwater behavior of island hydrology for hypothetical wet, dry, and median centuries. Our simulations show that water flow is greatest in drainages on the northwest and east coasts of the island. This correlates with some of the earliest and most persistent settlement on the island. During the most extreme droughts of the last 2000 years during the Medieval Climatic Anomaly (1150–600 cal BP), island populations contracted to a small number of large coastal villages. We argue that this was related in part to the greater availability of surface water at these locations. This study expands the theoretical and methodological scope of past studies that have applied hydrological simulation to archaeological investigations.     

The origin of Island mammoths and the quaternary land bridge history of the Northern Channel Islands,California

Pygmy proboscidean remains of Mammuthus exilis occur abundantly in late Quaternary deposits on the Northern Channel Islands, California. On the assumption that ancestral elephants could not have swum to the islands and must therefore have walked out, various land bridges have been hypothesized that link the northern islands to the mainland by a peninsula. Geological evidence for a land bridge, however, is lacking, and new evidence shows that elephants are excellent swimmers and skilled at crossing watergaps. The Santa Barbara Channel was narrowed to only 6 km during glacially lowered sea levels. Modern elephants swim much further, and at speeds ranging from 0.96–2.70 km/hr. Motives for California elephants to cross Pleistocene watergaps are inferred from motives that lead modern elephants in Asia and Africa to cross watergaps. These are the visual and olfactory sensing of islands and of insular food during times of drought or fire-induced food shortage. Diminutive size of M. exilis principally reflects lack of island predators, an adaption to periodic food stress in a finite forage area affected by periodic drought and fire, and an adaptation for keeping population numbers high to maintain genetic variability and to ensure survival despite accidents. A late Quaternary scenario describes the environmental setting of the Santa Barbara Channel and the conditions that led to proboscidean dispersal to the preexistent super-island Santarosae.     

Re-evaluating the origins of late Pleistocene fire areas on Santa Rosa Island,California, USA

At the close of the Pleistocene, fire regimes in North America changed significantly in response to climate change, megafaunal extinctions, anthropogenic burning and, possibly, even an extraterrestrial impact. On California's Channel Islands, researchers have long debated the nature of late Pleistocene “fire areas,” discrete red zones in sedimentary deposits, interpreted by some as prehistoric mammoth-roasting pits created by humans. Further research found no evidence that these red zones were cultural in origin, and two hypotheses were advanced to explain their origin: natural fires and groundwater processes. Radiocarbon dating, X-ray diffraction analysis, and identification of charcoal from six red zones on Santa Rosa Island suggest that the studied features date between ~ 27,500 and 11,400 cal yr BP and resulted from burning or heating, not from groundwater processes. Our results show that fire was a component of late Pleistocene Channel Island ecology prior to and after human colonization of the islands, with no clear evidence for increased fire frequency coincident with Paleoindian settlement, extinction of pygmy mammoths, or a proposed Younger Dryas impact event.     

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation, and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka Marine Terrace Chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized [White A. F., Schulz M. S., Vivit D. V., Blum A., Stonestrom D. A. and Anderson S. P. (2008) Chemical weathering of a Marine Terrace Chronosequence, Santa Cruz, California. I: interpreting the long-term controls on chemical weathering based on spatial and temporal element and mineral distributions. Geochim. Cosmochim. Acta72 (1), 36-68] and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisserand [Hellmann R. and Tisserand D. (2006) Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar. Geochim. Cosmochim. Acta70 (2), 364-383] or the aluminum inhibition model proposed by Oelkers et al. [Oelkers E. H., Schott J. and Devidal J. L. (1994) The effect of aluminum, pH, and chemical affinity on the rates of aluminosilicate dissolution reactions. Geochim. Cosmochim. Acta58 (9), 2011-2024], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site.Additionally, observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO₂(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws.     

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California I: Interpreting rates and controls based on soil concentration-depth profiles

The spatial and temporal changes in element and mineral concentrations in regolith profiles in a chronosequence developed on marine terraces along coastal California are interpreted in terms of chemical weathering rates and processes. In regoliths up to 15 m deep and 226 kyrs old, quartz-normalized mass transfer coefficients indicate non-stoichiometric preferential release of Sr > Ca > Na from plagioclase along with lesser amounts of K, Rb and Ba derived from K-feldspar. Smectite weathering results in the loss of Mg and concurrent incorporation of Al and Fe into secondary kaolinite and Fe-oxides in shallow argillic horizons. Elemental losses from weathering of the Santa Cruz terraces fall within the range of those for other marine terraces along the Pacific Coast of North America.Residual amounts of plagioclase and K-feldspar decrease with terrace depth and increasing age. The gradient of the weathering profile b_s is defined by the ratio of the weathering rate, R to the velocity at which the profile penetrates into the protolith. A spreadsheet calculator further refines profile geometries, demonstrating that the non-linear regions at low residual feldspar concentrations at shallow depth are dominated by exponential changes in mineral surface-to-volume ratios and at high residual feldspar concentrations, at greater depth, by the approach to thermodynamic saturation. These parameters are of secondary importance to the fluid flux q_h, which in thermodynamically saturated pore water, controls the weathering velocity and mineral losses from the profiles. Long-term fluid fluxes required to reproduce the feldspar weathering profiles are in agreement with contemporary values based on solute Cl balances (q_h = 0.025-0.17 m yr⁻¹).During saturation-controlled and solute-limited weathering, the greater loss of plagioclase relative to K-feldspar is dependent on the large difference in their respective solubilities instead of the small difference between their respective reaction kinetics. The steady-state weathering rate under such conditions is defined as

     

Siltstone from Southern Patagonia: Its Source and Archaeological Artifact Distribution in Santa Cruz Province,Argentina

Hunter‐gatherer mobility and spheres of interaction are important characteristics worthy of investigation in Patagonian archaeology. One way to approach these is by studying the distribution of lithic archaeological materials. Siltstone (limolite) artifacts are found along the western strip of southwestern Patagonia, Argentina. Based on geomorphological studies and the high density of archaeological material, a source was located along the western margin of Cardiel Lake. Neutron activation analysis of samples from the source and archaeological sites in several neighboring basins allowed us to model its circulation. Siltstone's archaeological distribution indicates that its regional circulation had a southerly direction dating from the early Holocene. This southern vector shows an important difference when compared to the distribution of obsidian from Pampa del Asador, which has a broader circulation pattern. This could be related to a greater availability of high‐quality lithic materials north of the siltstone source. This work also contributes to the construction of a lithic source database for southern Patagonia.     

Organic chemical characterization of sediment-trap particulates from San Nicolas,Santa Barbara,Santa Monica and San Pedro Basins,California

Particulate matter was collected during September–October, 1977, in particle traps suspended 30–60 m above the floor of San Nicolas, Santa Barbara, Santa Monica and San Pedro Basins, off the coast of southern California. The trap particulates were analyzed for C₁₅–C₃₅ hydrocarbons using gas chromatography (GC) and GC-mass spectrometry. Kerogens and humic acids were characterized by H/C, N/C, δ¹³C, δ¹⁵N and δ³⁴S ratios, and by electron-spin resonance. Hydrocarbons arising from fresh and weathered petroleum, marine autochthonous and terrestrial sources were identified. The rates of petroleum deposition during the collection period followed the order: San Nicolas Basin < Santa Barbara Basin ~ Santa Monica Basin < San Pedro Basin, with the largest amount of weathered petroleum being deposited in San Pedro Basin. The rates of petroleum deposition are correlated more strongly with human activities such as shipping, and the discharge of municipal and industrial wastes, than with natural submarine oil seepage. Analyses of kerogens and humic acids indicate that the majority of the organic matter in the trap particulates is of marine origin. The water column overlying Santa Barbara Basin appears to have the highest marine productivity of the four basins studied.     

Case study of compaction grouting for foundation support in karst terrain: Earth and Marine Sciences Building,University of California at Santa Cruz

Sinkholes were discovered during initial construction of a new science building at the University of California, Santa Cruz campus. The occurrence of such classic karst features in California is typically uncommon, although sinkholes have frequently been encountered at the campus during previous construction projects. Subsequent to the sinkhole collapse, geologic and engineering investigations were conducted to determine the size and extent of the collapsed sinkholes and assess the potential for further failure. An exploratory compaction grouting program was developed and implemented in order to locate, fill, and plug voids and to densify loose soils beneath the structure. Eighty-one injection locations were drilled, totaling 1350 m (4429 ft), and 248.2 m³ (324.4 yd³) of low-slump grout was placed. Grout volumes and pressures were carefully monitored, and these data correlated well with lithology determined during grout pipe drilling. Permitted movement on the structure was kept well within the allowable 0.64 cm (0.25 in) using a combination of manometers and laser levels.     

Fossil localities of the Santa Cruz Formation (Early Miocene,Patagonia, Argentina) prospected by Carlos Ameghino in 1887 revisited and the location of the Notohippidian

Between January and September of 1887 Carlos Ameghino carried out his first geologic and paleontological expedition to the Río Santa Cruz, Patagonia. Based on the fossils and geologic information compiled, in 1887 and 1889, Florentino Ameghino named more than 120 new species of extinct mammals and his Formación Santacruceña and Piso Santacruceño (Santacrucian stage). Data published by both brothers state that the specimens were collected in outcrops by the Río Santa Cruz, between 90 and 200 km west of its mouth. However, information in the posthumously published letters and Travel Diary of C. Ameghino allows us to recognize a fourth locality, Río Bote, at about 50 km further southwest. In 1900, 1902, F. Ameghino divided the Piso Santacruceño in a younger étage Santacruzienne and older étage Notohippidéen, restricting the geographical distribution of the latter to Kar Aiken locality, northeast of Lago Argentino. However, 15 of the 54 species that F. Ameghino listed as exclusively Notohippidian stage already had been named on specimens collected South to the Río Santa Cruz in 1887, two year prior to C. Ameghino's first visit to Kar Aiken. Based on historical information and several expeditions to the Río Santa Cruz and its environs, in this contribution we establish the geographical locations of the 1887 localities, formalize their names, evaluate the stratigraphic position of the fossil-bearing levels, and analyze the geographic extension of the Notohippidian, inferring that Río Bote is where C. Ameghino first collected species that came to define the Notohippidian.     

A 560-Year Record of Santa Ana Fires Reconstructed from Charcoal Deposited in the Santa Barbara Basin, California

Microscopic charcoal from varved Santa Barbara Basin sediments was used to reconstruct a 560-yr record (A.D. 1425 to 1985) of Santa Ana fires. Comparison of large (>3750 μm²) charcoal with documented fire records in the Santa Barbara Ranger District shows that high accumulations correspond to large fires (>20,000 ha) that occurred during Santa Ana conditions. The charcoal record reconstructed a minimum of 20 large fires in the Santa Barbara region during the study period. The average time between fires shows no distinct change across three different land use periods: the Chumash period, apparently characterized by frequent burning, the Spanish/Early American period with nominal fire control, and the 20th century with active fire suppression. Pollen data support the conclusion that the fire regime has not dramatically changed during the last 500 yr. Comparison of large charcoal particle accumulation rates and precipitation reconstructed from tree rings show a strong relationship between climate and fire history, with large fires consistently occurring at the end of wet periods and the beginning of droughts.     

A morphometric analysis of terrace gravels in Santa Ynez basin,Santa Barbara County,California

An analysis of 6,300 pebbles from eighteen river terraces within the five subareas of the Santa Ynez River basin has revealed significant differences in particle sphericity and roundness of the various terrace gravels.Using the Cailleux technique of pebble measurement, Krumbein's sphericity ratio formula (Y) and the author's own roundness ratio or the I/L¹ ratio (R) the computed values derived for $\text{Y}$ range from 0.92 to 1.11, and for $\text{R}$ from 0.66 to 0.79 on these benches.An analysis of variance, based on the F-test applied to samples has established that: (a) gravel sphericity and roundness increase significantly from upstream to the river mouth; (b) in the subareas themselves pebble sphericity and roundness vary significantly from bench to bench indicating varied energy conditions of deposition; (c) all terrace gravels measured show higher sphericity and roundness than the underlying Orcutt gravels. This suggests a reworking of the latter by the Santa Ynez River.     

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California. Part II: Solute profiles, gradients and the comparisons of contemporary and long-term weathering rates

The spatial and temporal changes in hydrology and pore water elemental and ⁸⁷Sr/⁸⁶Sr compositions are used to determine contemporary weathering rates in a 65- to 226-kyr-old soil chronosequence formed from granitic sediments deposited on marine terraces along coastal California. Soil moisture, tension and saturation exhibit large seasonal variations in shallow soils in response to a Mediterranean climate. These climate effects are dampened in underlying argillic horizons that progressively developed in older soils, and reached steady-state conditions in unsaturated horizons extending to depths in excess of 15 m. Hydraulic fluxes (q_h), based on Cl mass balances, vary from 0.06 to 0.22 m yr⁻¹, resulting in fluid residence times in the terraces of 10-24 yrs.As expected for a coastal environment, the order of cation abundances in soil pore waters is comparable to sea water, i.e., Na > Mg > Ca > K > Sr, while the anion sequence Cl > NO₃ > HCO₃ > SO₄ reflects modifying effects of nutrient cycling in the grassland vegetation. Net Cl-corrected solute Na, K and Si increase with depth, denoting inputs from feldspar weathering. Solute ⁸⁷Sr/⁸⁶Sr ratios exhibit progressive mixing of sea water-dominated precipitation with inputs from less radiogenic plagioclase. While net Sr and Ca concentrations are anomalously high in shallow soils due to biological cycling, they decline with depth to low and/or negative net concentrations. Ca/Mg, Sr/Mg and ⁸⁷Sr/⁸⁶Sr solute and exchange ratios are similar in all the terraces, denoting active exchange equilibration with selectivities close to unity for both detrital smectite and secondary kaolinite. Large differences in the magnitudes of the pore waters and exchange reservoirs result in short-term buffering of the solute Ca, Sr, and Mg. Such buffering over geologic time scales can not be sustained due to declining inputs from residual plagioclase and smectite, implying periodic resetting of the exchange reservoir such as by past vegetational changes and/or climate.Pore waters approach thermodynamic saturation with respect to albite at depth in the younger terraces, indicating that weathering rates ultimately become transport-limited and dependent on hydrologic flux. Contemporary rates R_solute are estimated from linear Na and Si pore weathering gradients b_solute such that

     

Fire and vegetation history on Santa Rosa Island,Channel Islands,and long‐term environmental change in southern California

The long‐term history of vegetation and fire was investigated at two locations – Soledad Pond (275 m; from ca. 12 000 cal. a BP) and Abalone Rocks Marsh (0 m; from ca. 7000 cal. a BP) – on Santa Rosa Island, situated off the coast of southern California. A coastal conifer forest covered highlands of Santa Rosa during the last glacial, but by ca. 11 800 cal. a BP Pinus stands, coastal sage scrub and grassland replaced the forest as the climate warmed. The early Holocene became increasingly drier, particularly after ca. 9150 cal. a BP, as the pond dried frequently, and coastal sage scrub covered the nearby hillslopes. By ca. 6900 cal. a BP grasslands recovered at both sites. Pollen of wetland plants became prominent at Soledad Pond after ca. 4500 cal. a BP, and at Abalone Rocks Marsh after ca. 3465 cal. a BP. Diatoms suggest freshening of the Abalone Rocks Marsh somewhat later, probably by additional runoff from the highlands. Introduction of non‐native species by ranchers occurred subsequent to AD 1850. Charcoal influx is high early in the record, but declines during the early Holocene when minimal biomass suggests extended drought. A general increase occurs after ca. 7000 cal. a BP, and especially after ca. 4500 cal. a BP. The Holocene pattern closely resembles population levels constructed from the archaeological record, and suggests a potential influence by humans on the fire regime of the islands, particularly during the late Holocene. Copyright © 2009 John Wiley & Sons, Ltd.     

New evidence concerning the Plio-Pleistocene landscape evolution of southern Santa Cruz region

Remnants of an old aggradational landscape, Cerro Cuadrado Proglacial, are preserved on top of the high mesetas Pampa Alta and La Meseta on both sides of the upper Santa Cruz river valley, South Patagonia.A first dissection of the mesetas, attributable to extended river erosion, predates the expansion of glacier lobes down the piedmontane area. The glacial advance is represented by the moraines of Pampa Alta Glaciation displayed on the top of Meseta Pampa Alta. Glacifluvial outlets contribute to the proglacial plain, Pampa Alta Proglacial, which is widespread to the southeast.Strong and persistent fluvial erosion followed the retreat of the ice masses leading to the formation of several terrace levels in the main upper valley, La Australasia Terraces and San Fernando Terraces, and a step, Cordón Alto, that truncates the Meseta Pampa Alta. These foreland features and the relief covered by the basalts at Cerro Fraile in the cordillera, are probably a consequence of a diastrophic phase that affected both areas during this stage.Late Pliocene basaltic lavas draining into the main and tributary valleys overran this landscape. The evidence indicates that during the eruption of the basalts the glaciation was active in the cordillera and that coeval fluvial and lacustrine aggradation took place in the extra-andean valleys.During the Middle Pleistocene subsequent lava flows covered the high pampas and partially occupied the fluvial valleys again. After this last volcanic episode the glaciers reached their maximum expansion to the east.     

Particulate iron and manganese in the Santa Barbara Basin,California

Particulate Fe and Mn may be important trace metal scavengers in the water column as well as being probable indicators of biologically mediated redox processes. A study has been made of suspended particulate composition in the Santa Barbara Basin, a shallow near-shore basin off southern California with sub-oxic conditions below sill depth. Observations have revealed several interesting phenomena relating to the geochemistry of Fe and Mn. Most striking is a profound enrichment of particulate Fe in samples from the bottom two hundred meters. These particulates have a constant Fe/P mole ratio of about three and may originate at the sediment-water interface or may be transported to the basin from local marshes. For particulate Mn, enrichments are observed both in the sub-sill waters and near the base of the euphotic zone. A consideration of particle removal rates suggests that the sub-photic zone enrichment has a biogenic origin. In the sub-sill waters, enrichment in Mn is apparently due to the precipitation of dissolved Mn diffusing from the anoxic basin sediments. A simple mass balance suggests that most of the Mn lost from the sediments is transported from the Santa Barbara Basin in dissolved form.