Symposium on Chemical and Biological Characterization of Municipal Sludges, Sediments, Dredge Spoils, and Drilling Muds : abstracts, May 20-22, 1986.

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Fate and effects of drilling wastes in a shallow estuarine mesocosm

To address concerns expressed about the possible effect of drilling mud discharges on shallow, low-energy estuarine ecosystems, a 12 month study was designed to detect alterations in water quality and sediment geochemistry. Each drilling mud used in the study and sediments from the study site were analyzed in the laboratory for chemical and physical characteristics. Potential water quality impacts were simulated by the EPA-COE elutriation test procedure. Mud toxicity was measured by acute and chronic bioassays with Mysidopsis bahia, Mercenaria mercenaria, and Nereis virens.^ For the field study, a relatively pristine, shallow (1.2 m) estuary (Christmas Bay, TX) without any drilling activity for the last 30 years was chosen for the study site. After a three month baseline study, three stations were selected. Station 1 was an external control. At each treatment station (2, 3), mesocosms were constructed to enclose a 3.5 m$\sp3$ water column. Each treatment station included an internal control site also. Each in situ mesocosm, except the controls, was successively dosed at a mesocosm-specific dose (1:100; 1:1,000; or 1:10,000 v/v) with 4 field collected drilling muds (spud, nondispersed, lightly-treated, and heavily-treated lignosulfonate) in sequential order over 1.5 months. Twenty-four hours after each dose, water exchange was allowed until the next treatment. Station 3 was destroyed by a winter storm. After the last treatment, the enclosures were removed and the remaining sites monitored for 6 months. One additional site was similarly dosed (1:100 v/v) with clean dredged sediment from Christmas Bay for comparison between dredged sediments and drilling muds.^ Results of the analysis of the water samples and field measurements showed that water quality was impacted during the discharges, primarily at the highest dose (1:100 v/v), but that elevated levels of C, Cr (T,F), Cr$\sp{+3}$ (T, F), N, Pb, and Zn returned to ambient levels before the end of the 24 hour exposure period or immediately after water exchange was allowed (Al, Ba(T), Chlorophyll ABC, SS, %T). Barium, from the barite, was used as a geochemical tracer in the sediments to confirm estimated doses by mass balance calculations. Barium reached a maximum of 166x background levels at the high dose mesocosm. Barium levels returned to ambient or only slightly elevated levels at the end of the 6 month monitoring period due to sediment deposition, resuspension, and bioturbation. QA/QC results using blind samples consisting of lab standards and spiked samples for both water and sediment matrices were within acceptable coefficients of variation.^ In order to avoid impacts on water quality and sediment geochemistry in a shallow estuarine ecosystem, this study concluded that a minimal dilution of 1:1,000 (v/v) would be required in addition to existing regulatory constraints. ^

(Table 1) Uranium at DSDP Hole 69-504B pore water

Basalt formation waters collected from Hole 504B at sub-basement depths of 194, 201, 365, and 440 meters show inverse linear relationships between 87Sr/86Sr and Ca, 87Sr/86Sr and Sr, and K and Ca. If the Ca content of a fully reacted formation water end-member is assumed to be 1340 ppm, the K, Sr, and 87Sr/86Sr values for the end-member are 334 ppm, 7.67 ppm, and 0.70836, respectively. With respect to contemporary seawater at Hole 504B, K is depleted by 13%, Sr is enriched by 2.7%, and 87Sr/86Sr is depleted by 0.8%. The Sr/Ca ratio of the formation water (0.0057) is much lower than that of seawater (0.018) but is similar to the submarine hot spring waters from the Galapagos Rift and East Pacific Rise and to geothermal brines from Iceland. At the intermediate temperatures represented by the Hole 504B formation waters (70°-105°C), the interaction between seawater and the ocean crust produces large solution enrichments in Ca, the addition of a significant basalt Sr isotope component accompanied by only a minor elemental Sr component, and the removal from solution of seawater K. The Rb, Cs, and Ba contents of the formation waters appear to be affected by contamination, possibly from drilling muds.

(Table 1) Stratigraphic position, abundance, shape, color, and refractive indices of glass shards of selected samples from DSDP Leg 60 Holes vitric muds

Precisely determined refractive indices of glass shards from 32 ash-rich, volcaniclastic sediments, mostly turbidites interbedded with nonvolcanic sediments in the Mariana Trough, range from 1.480 to 1.585 (corresponding to SiO2 ca. 75 to 49%), with most in the range 1.500 to 1.540 (SiO2 ca. 70-62%) and a second, smaller mode between ca. 1.560 and 1.585 (57 to 49% SiO2). Shards are almost exclusively colorless from 1.480 to ca. 1.530, light brown with minor colorless and green tones between 1.530 and 1.560, and dominantly brown at higher refractive indices. Tubular pumice shards are more common at higher silica percentages and non- to poorly-vesicular cuniform shards at low SiO2 values, but there is no clear correlation between shape and composition of shards. About half of the samples have bimodal shard populations with silica differences ranging up to 20 percent; unimodal layers have a range of up to about 7 percent SiO2. Of 21 samples in which one type of shard dominates, seven have the main mode in the rhyolitic composition (>69% SiO2), eight in the intermediate range (56 to 69% SiO2), and five in mafic composition (SiO2 <53%). These unusually abundant mafic shards occur mainly in site survey piston cores, SP-IA and 4E, and in Holes 454, 456, 458, and 459B. These are the sites closest to the present arc. Hole 453, containing by far the most vitric tuff turbidites, shows a gradual increase in silica content of ash layers upward to the hole from Cores 36 to 19 (about 4.6 to 3.0 Ma). A drastic decrease in ash-rich beds in the younger (Pleistocene) part of this hole was noted by the shipboard party (see site chapter, Site 453) and was interpreted by them as indicating increasing distance from the arc volcanoes as the trough opened. The increase in silica in ashes from the early to the late Pliocene at Site 453 could be interpreted in the same way and might indicate that the trough started to open in early Pliocene time.

Mineralogy of serpentine muds of ODP Leg 125 holes (Table 1)

Large serpentinite seamounts are common in the forearc regions between the trench axis and the active volcanic fronts of the Mariana and Izu-Bonin intraoceanic arcs. The seamounts apparently form both as mud volcanoes, composed of unconsolidated serpentine mud flows that have entrained metamorphosed ultramafic and mafic rocks, and as horst blocks, possibly diapirically emplaced, of serpentinized ultramafics partially draped with unconsolidated serpentine slump deposits and mud flows. The clayand silt-sized serpentine recovered from three sites on Conical Seamount on the Mariana forearc region and from two sites on Torishima Forearc Seamount on the Izu-Bonin forearc region is composed predominantly of chrysotile, brucite, chlorite, and clays. A variety of accessory minerals attest to the presence of unusual pore fluids in some of the samples. Aragonite, unstable at the depths at which the serpentine deposits were drilled, is present in many of the surficial cores from Conical Seamount. Sjogrenite minerals, commonly found as weathering products of serpentine resulting from interaction with groundwater, are found in most of the samples. The presence of aragonite and carbonate-hydroxide hydrate minerals argues for interaction of the serpentine deposits with fluids other than seawater. There are numerous examples of sedimentary serpentinite deposits exposed on land that are very similar to the deposits recovered from the serpentine seamounts drilled on ODP Leg 125. We suggest that Conical Seamount may be a type locality for the study of in situ formation of many of these sedimentary serpentinite bodies. Further, we suggest that both the deposits drilled on Conical Seamount and on Torishima Forearc Seamount demonstrate that serpentinization can continue in situ within the seamounts through interaction of the serpentine deposits with both seawater and subduction-related fluids.

Ultimate and failure strengths of normal muds and serpentinite muds of ODP Leg 125 samples

Serpentinite seamounts in the Mariana forearc have been explained as diapirs rising from the Benioff zone. This hypothesis predicts that the serpentinites should have low strengths as well as low densities relative to the surrounding rocks. Drilling during Leg 125 showed that the materials forming Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc are water-charged serpentinite muds of density <2 g/cm**3. Wykeham-Farrance torsion-vane tests showed that they are plastic solids with a rheology that bears many similarities to the idealized Cam clay soil model and is well described by critical-state soil mechanics. The serpentinite muds have ultimate strengths of 1.3 to 273.7 kPa and yield strengths of approximately 1.0 to 50 kPa. These muds thus are orders of magnitude weaker than salt and are, in fact, comparable in density and strength to common deep-sea clay muds. Such weak and low-density materials easily become diapiric. Serpentinite muds from the summit of Conical Seamount are weaker and more ductile than those on its flanks or on Torishima Forearc Seamount. Moreover, the summit muds do not contain the pronounced pure- and simple-shear fabrics that characterize those on the seamount flanks. The seamounts are morphologically similar to shield volcanoes, and anastomosing serpentinite debris flows descending from their summits are similar in map view to pahoehoe flows. These morphologic features, together with the physical properties of the muds and their similarities to other oceanic muds and the geochemistry of the entrained waters, suggest that many forearc serpentinite seamounts are gigantic (10-20 km wide, 1.5-2.0 km high) mud volcanoes that formed by the eruption of highly liquid serpentinite muds. Torishima Forearc Seamount, which is blanketed by more ìnormalî pelagic/volcaniclastic sediment, has probably been inactive since the Miocene. Conical Seamount, which seems to consist entirely of serpentinite mud and is venting fresh water of unusual chemistry from its summit, is presently active. Muds from the flanks of Conical Seamount are stronger and more brittle than those from the summit site, and muds from Torishima Forearc Seamount are stronger yet; this suggests that the serpentinite debris flows are compacted and dewatered as they mature. The shear fabrics probably result from downslope creep and flow, but may also be inherited.

Major and trace element composition of sepentine muds and metabasic rocks of ODP Leg 195 and Leg 125 sites

New geochemical data on serpentinite muds and metamorphic clasts recovered during Ocean Drilling Program Legs 195 (Holes 1200A-1200E) and 125 (Holes 778A and 779A) provide insights into the proportions of rock types of various sources that compose the serpentinite mudflows and the fluid-rock interactions that predominate in these muds. We interpret the metamorphic rock fragments as derivatives of mostly metamorphosed mafic rocks from the descending Pacific oceanic crust. Based on their mid-ocean-ridge basalt (MORB)-like Al2O3, TiO2, CaO, Si/Mg, and rare earth element (REE) systematics, these metamorphic rocks are classified as metabasalts/metagabbros and, therefore, ~30-km depths represent an active subduction zone setting. The serpentinite muds from Holes 1200A and 1200E have slightly lower REE when compared to Hole 1200D, but overall the REE abundance levels range between 0.1-1 x chondrite (CI) levels. The chondrite-normalized patterns have [La/Sm]N ~ 2.3 and [Sm/Yb]N ~ 2. With the exception of one sample, the analyzed metamorphic clasts show flat to slightly depleted light REE patterns with 1.0-15 x CI levels, resembling MORBs. Visually, ~6 vol% of the serpentinized muds are composed of 'exotic' materials (metamorphic clasts [schists]). Our mixing calculations confirm this result and show that the serpentinite muds are produced by additions of ~5% metamafic materials (with flat and up to 10 x CI REE levels) to serpentinized peridotite clast material (with very low REE abundances and U-shaped chondrite-normalized patterns). The preferential incorporation of B, Cs, Rb, Li, As, Sb, and Ba into the structure of H2O-bearing sheet silicates (different than serpentine) in the Leg 125 and Leg 195 metamorphic clasts (chlorite, amphibole, and micas) have little effect on the overall fluid-mobile element (FME) enrichments in the serpentinite muds (average B = ~13 ppm; average Cs = ~0.05 ppm; average As = ~1.25 ppm). The extent of FME enrichment in the serpentinized muds is similar to that described for the serpentinized peridotites, both recording interaction with fluids very rich in B, Cs, and As originating from the subducting Pacific slab.

Geochemistry of ODP Site 131-808 muds and mudstones

The principal aims of undertaking a shore-based bulk inorganic geochemical analysis of muds and mudstones from Site 808 were as follows: 1. Characterize the geochemical signature of the muds and mudstones at regular intervals downhole to sample and identify any changes in sediment type and provenance. 2. Integrate the inorganic geochemistry with the shipboard and more detailed land-based laboratory studies of the clay minerals. 3. Investigate any possible inorganic geochemical anomalies associated with the décollement.

Diagenetic dolomite formation in Quaternary anoxic diatomaceous muds at DSDP Leg 64 Holes

During drilling in the Gulf of California, diagenetic carbonate rocks were recovered at 7 out of 8 sites. These are primarily dolomites which record 13C isotopic evidence of the incorporation of carbon derived from the decomposition of organic matter. In Hole 479, drilled to a sub-bottom depth of 440 meters on the Guaymas Slope, under a fertile upwelling belt, we recognized an excellent example of deep sea dolomitization in progress. This Quaternary section of organic-carbon- rich, low-carbonate, hemipelagic diatomaceous oozes contains numerous fine-grained, decimeter-thin, episodic beds of dolomite, which show sedimentologic, geochemical, and isotopic evidence of accretion by precipitation below 40 meters sub-bottom in zones of high alkalinity and low sulfate. The beds preserve original sedimentary structures. Carbon-13 varies from +3 to +14 per mil, indicating biogenic CO2 reservoirs related to active methanogenesis. In single beds, 18O values range outwardly from +5 to -7 per mil, reflecting increasing temperature with progressive accretion of dolomite with depth; the values parallel progressive trends in lithification, texture, mineralogy, and fossil preservation. We estimate slow accretion rates on the order of 0.1-0.7 mm/10**3 yr. with burial. Dolomitization does not proceed merely at the expense of nearby nannofossils. Ca and Mg ions must be derived from interstitial waters. The episodic appearance of beds in the sequence seems partly a reflection of latent climate signals. This process of deep sea dolomitization carries implications for hydrocarbon migration, as well as an interpretation of the presence of dolomite in other modern and ancient pelagic to hemipelagic sediment sequences.

Geochemistry of serpentine muds of ODP Leg 125 holes

The <63-µm fractions of serpentinite muds from two seamounts on the Mariana and Izu-Bonin forearcs were analyzed for mineral composition by X-ray diffraction and for chemical composition by X-ray fluorescence. The silt fraction of the muds consists predominantly of chrysotile, brucite, and ample amorphous constituents. Chlorite and smectite are less abundant components. Of special interest is the occurrence of iowaite, a brucite-like, Cl-bearing mineral with a layered structure. Iowaite was not found in the samples from the summit site of one of the seamounts drilled; however, it is scattered throughout the strata, composing the flanks of both seamounts investigated. No systematic change of the iowaite abundance with depth was observed. The distribution of iowaite is confined to the surface of the flanks of the seamount. Based on the distribution on the mineral and its chemical composition, we suggest that the iowaite formed by oxidation of some of the ferrous iron in brucite contained in the serpentine mud as it contacted abyssal seawater during protrusion onto the seafloor. The resulting positive charge imparted to the brucite was compensated by the uptake of seawater chloride. Consequently, the formation of iowaite is restricted to the seafloor where oxygen and chloride are available for these reactions. The availability of oxygen is considered the limiting factor. We conclude that iowaite formation cannot be a major cause for the low chlorinity of pore fluids inside the seamounts.